Production method of silver halide photographic emulsion and production apparatus thereof

ABSTRACT

At least one of a nucleus forming process, a nucleus growing process, a chemical sensitizing process, and a spectral sensitizing process for producing a silver halide photographic emulsion is performed by using a microreactor. A minute region of the microreactor is used to precisely perform a reaction of nucleus formation. A condition under which host grains are allowed to react with newly supplied silver halide nuclei is made uniform to cause uniform crystal growth. A predetermined quantity of molecules for chemical sensitization is doped in a crystal lattice of a nucleus of silver halide to effect a sensitizing process. Alternatively, a spectral sensitizing process in which a single molecular layer of a spectral sensitizer is uniformly adsorbed on a silver halide nucleus grain surface is securely carried out.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a production method of silverhalide photographic emulsion in which reaction, mixing or the like in aproduction process of silver halide photographic emulsion is carried outby a chemical unit operation, and a production apparatus thereof.

[0003] 2. Description of the Related Art

[0004] In general, a silver halide photographic emulsion used for aphotosensitive material is produced through a pre-ripening process inwhich a nucleus forming process (formation of a microcrystal dispersionof silver halide in protective colloid), a physical ripening process(crystal growth for obtaining a desired grain shape and size), and acrystal growth process are performed to form silver halide photographicemulsion grains having an objective size, shape and structure, adesalting process (removal of soluble salts from the dispersion), asensitizing process (heat treatment performed in the presence of asensitizing agent, for increasing sensitivity to light) for increasingthe sensitivity of the emulsion after desalting, and a after-ripeningprocess for adding various agents (sensitizing dye, stabilizing agent,and etc.) for giving various properties to the emulsion required as theneed arises.

[0005] Incidentally, in the foregoing production process of the silverhalide photographic emulsion, two or more processes among theseprocesses, may be combined and carried out in one operation. Further, inthe foregoing production process, one or more production stages may beomitted from the production process. Furthermore, there is also a casewhere plural operations are repeated in each stage in order to obtain adesired emulsion.

[0006] In addition, in a production system for industriallymass-producing silver halide emulsion, a so-called batch type productionsystem using a large capacity reaction container is usually used.

[0007] As a conventional batch-type production system for producingsilver halide emulsion, there is proposed one using a tank 10 as areaction container as exemplified in FIG. 37 (for example, see JP-A No.5-173267).

[0008] This tank 10 is constituted as a batch type reaction containerapparatus having an agitator capable of producing of silver halidephotographic emulsion at a time in a predetermined large amount, forexample, 1000 l (1 t)

[0009] In this tank 10, in order to agitate a solution with which thetank is filled, a magnetic agitation means 16 is provided such that anagitation vane 12 is rotatively driven through a transmission means 14for transmitting a rotation driving force of a motor 15 in a non-contactmanner by using a magnetic force.

[0010] In addition, in order to perform a temperature control of thesolution with which the tank is filled, a temperature control means 18for heating or cooling the reaction solution is disposed at the outerperipheral part of the tank 10. The temperature control means 18 isconstituted by use of means for heating or cooling by allowing a heatexchange medium (water, water vapor, liquid organic material, flame gas,etc.) to flow to a temperature control part, or a means for performing atemperature control by installing an element for electrically heating orcooling at the temperature control part.

[0011] The tank 10 is constituted to be capable of being hermeticallyclosed by mounting a sealing lid 20 to the tank 10. Further, an emulsionintroduction pipe 22 with an opening and closing cock is disposed in thesealing lid 20 of the tank 10. Furthermore, a liquid transfer pipe 24with an opening and closing cock is disposed at the bottom of the tank10.

[0012] In the butch type production system using this tank 10, at thenucleus forming process in the pre-ripening process at the time ofproducing a silver halide emulsion, a predetermined quantity of anaqueous dispersion medium solution containing at least a dispersionmedium and water is injected through the emulsion introduction pipe 22into the tank 10, and further, a silver salt solution or a silver saltsolution and a halide solution are added under the conditions of pBr 2.5or less and are agitated by the magnetic agitation means 16 for apredetermined time (several minutes), and temperature is controlled bymeans of a temperature control means 18 so as to keep the reactionsolution in the tank 10 within a predetermined temperature range (forexample, 5° C. to 45° C.), so that nuclei of minute tabular grainsincluding, for example, a parallel twinning plane are formed.

[0013] In this nucleus forming process, since solute ions are randomlywalking in the solution when the nuclei are formed, minute tabular grainnuclei and a large number of other minute grains (especially, non-twin,single twin, or non-parallel double twin grains) are simultaneouslyformed in the tank 10.

[0014] Next, in the butch-type production system using this tank 10, atthe ripening process in the pre-ripening process at the time when thesilver halide photographic emulsion is produced, grains other than thetabular grain nucleus are made to disappeared by the Ostwald ripeningprocess, and the tabular grain nucleus is made to grow.

[0015] In this ripening process, three ripening methods that haveconventionally been used described below can be used. The first type ofthe ripening method is a method in which after nucleus formation, a pBrvalue of the reaction solution in the tank 10 is adjusted to 2.5 to 1.0,preferably 2.3 to 1.4, a solvent for AgX is added through the emulsionintroduction pipe 22 (AgNO₃ may be added during the ripening), agitationis performed by the magnetic agitation means 16, and the temperature ofthe reaction solution in the tank 10 is raised by the temperaturecontrol means 18 by preferably 10° C. or higher, more preferably 20° C.or higher with respect to the nucleus formation temperature, sob thatripening is performed for predetermined several minutes or more.

[0016] The second type of the ripening method is a method in which afternucleus formation, a pBr value of the solution is adjusted to 2.5 orless, preferably 1.0 to 2.0, a first ripening is performed forpredetermined several minutes or more in a state where there is nosolvent for AgX, and next, AgNO₃ is added through the emulsionintroduction pipe 22 to increase the pBr value by 0.1 or more,preferably 0.3 or more, the solvent for AgX is added through theemulsion introduction pipe 22, agitation is performed by the magneticagitation means 16, and the temperature of the reaction solution in thetank 10 is raised by the temperature control means 18 by preferably 10°C or higher, more preferably 20° C. or higher with respect to thenucleus formation temperature, so that second type of ripening isperformed for predetermined several minutes or more.

[0017] The third type of ripening method is a method in which afternucleus formation, a pBr value of the solution is adjusted to 2.5 orless, preferably 1.0 to 2.0, agitation is performed by the magneticagitation means 16 in a state where there is no solvent for AgX, thetemperature of the reaction solution in the tank 10 is raised by thetemperature control means 18 by preferably 10° C. or higher, morepreferably 20° C. or higher with respect to the nucleus formationtemperature, so that the third type of ripening is performed forpredetermined several minutes or more. Incidentally, there is also amethod in which AgNO₃ is added during the ripening.

[0018] Further, in the foregoing first to third type of ripeningmethods, there is also a method using a pressure ripening method inwhich the tank 10 is made a hermetically sealed system only at the timeof ripening, and ripening is performed in a state where the pressure inthe tank 10 at the time of nucleus ripening is more than several timesas high as the atmospheric pressure. Further, there is also a method inwhich the ripening is performed by the foregoing first to third ripeningmethods in the presence of an anti-fogging agent.

[0019] Next, in the batch type production system using this tank 10,after the ripening process in the pre-ripening process at the time ofproduction of the silver halide emulsion has been ended, tabular grainnuclei are made to grow in the crystal growth process.

[0020] In the crystal growth process, it is possible to use a method ofadding a silver salt solution and a halide solution as a solute forgrowing a crystal of tabular grain nuclei, a flow acceleration additionmethod, a concentration acceleration addition method, and a combinedaddition method of two or more of these methods.

[0021] In the butch type production system using this tank 10, also atthe crystal growth stage in the pre-ripening process at the time ofproduction of the silver halide emulsion, a predetermined quantity ofsilver salt solution and halide solution as solutes for growing thecrystals of the tabular grain nuclei is injected from the emulsionintroduction pipe 22 into the reaction solution stored in the tank 10,agitation is performed by the magnetic agitation means 16 for apredetermined time (several minutes), a temperature control is performedby the temperature control means 18 to bring the reaction solution inthe tank 10 to a predetermined temperature, and a chemical reaction forsuitably allowing to grow crystals is accelerated (see, for example,Japanese Patent Application Nos. 2-142635 and 2-43791).

[0022] In the batch type production system using this tank 10, after thecrystal growth process in the pre-ripening process at the time ofproduction of the silver halide emulsion has been ended, the desaltingprocess is carried out.

[0023] The desalting process is a process of removing unnecessarymaterials (for example, K, Na) formed during the emulsion grainformation of the pre-ripening process, excessively existing ions (forexample, Ag, Br, Cl) and the like.

[0024] In the desalting process, various desalting methods, such as aflocculation method or a noodle washing method in which water washing isperformed to effect desalting, or an ultrafiltration or an electrodialysis method in which desalting is carried out by separation (film),can be used.

[0025] In the desalting process, for example, in the case where theflocculation method is used, the reaction solution which has beensubjected to the pre-ripening process in the tank 10 as shown in FIG. 37is taken out from the liquid transfer pipe 24, and is transferred to adesalting tank (not-show), and a flocculant is added to the reactionsolution in the desalting tank, and a pH value of the solution isadjusted, so that emulsion grains together with gelatin, areflocculating-sedimented (natural sedimentation), a supernatant liquidcontaining unnecessary materials is removed, and next, after washingwater is newly added into the desalting tank, the flocculation ofgelatin is deflocculated by adjusting pH value of the solution. Theseprocesses are repeated two or three times.

[0026] Further, in this batch type production system, after thedesalting process at the time of production of the silver halideemulsion has been ended, an after-ripening process is carried out. Thisafter-ripening process is a process in which the emulsion having a lowsensitivity in the reaction solution after desalting process issensitized to impart sensitivity suitable for practical use.

[0027] In the sensitizing method at the after-ripening process in thebatch type production system, there are a chemical sensitizing methodand a spectral sensitizing method. The chemical sensitizing method is amethod for increasing the intrinsic sensitivity of the emulsion. Atypical chemical sensitizing method includes three kinds of methods,that is, a sulfur sensitizing method, a gold sensitizing method and areduction sensitizing method.

[0028] In the case where this chemical sensitizing method is performed,the reaction solution which has been subjected to the desalting processis transferred to a tank as a reaction container (not-shown) constitutedsimilarly to the foregoing tank 10, a chemical sensitizing agent ismetered and a predetermined quantity of the agent is added through anagent introduction pipe to the reaction solution stored in the tank. Anagitation vane stirs the solution, and the temperature of the solutionis controlled by a temperature control means so that the chemicalsensitizing agent is uniformly distributed to emulsion grains tocomplete a desired chemical reaction equally.

[0029] In addition, the spectral sensitizing method as the sensitizingmethod in the after-ripening process is a method in which in the casewhere the emulsions are used in a color photosensitive material or thelike, sensitizing wavelength ranges are respectively widened into thewavelength ranges of the three primary colors of light, that is, blue(400 to 500 nm), green (500 to 600 nm), and red (600 to 700 nm) from theintrinsic sensitivities of the emulsions in the reaction solutions.

[0030] The spectral sensitizing method is generally performed byadsorbing a sensitizing dye onto an emulsion. As the sensitizing dyeused here, there is an orthochromatic sensitizing dye (for green) or apanchromatic dye (for red). The sensitizing dyes are dissolved inmethanol to form a solution, or are made a dye solid dispersed solutionin gelatin, and are added to the emulsion as the reaction solution.

[0031] Incidentally, the dye solid dispersed solution in gelatin isprepared at a preparation process, and is temporarily refrigerated, andat the time of use, it is melted to add to the emulsion.

[0032] When the spectral sensitizing method is used, the reactionsolution which has been subjected to the desalting process istransferred to a tank as a reaction container (not-shown) constitutedsimilarly to the foregoing tank 10, a solution in which a sensitizingdye is dissolved in methanol or a solution in which a sensitizing dye ismade to a solid dispersed solution in gelatin (this solid dispersedsolution in gelatin is prepared at a preparation process, is temporarilyrefrigerated, is melted at the time of use to be added to the emulsion)is metered and a predetermined quantity of solution is added through anagent introduction pipe to the reaction solution stored in the tank. Thesolution is stirred well by an agitation vane, the temperature of thesolution is controlled by a temperature control means so that thechemical sensitizing agent is uniformly distributed to the emulsiongrains and is uniformly adsorbed by the grains.

[0033] In this batch type production system, after the after-ripeningprocess in the production processes of the silver halide emulsion hasbeen completed, a storage process is performed. The storage process is aprocess of temporarily storing the emulsion prepared in the batchoperation for the purpose of supplying the emulsion to an emulsioncoating process in continuous operation.

[0034] Further, in addition to the function of temporal storage, thisstorage process also provides a function to stop the progress ofripening by cooling the emulsion to eliminate differences incharacteristics among emulsion preparation batches by batch-blending aplurality of the same kind emulsions, as well as a function for qualityassurance by measuring physical properties of the prepared emulsions toassure the characteristics of the emulsions.

[0035] Thus, in the batch type production system, the equipment for thestorage process is constituted by a cooling apparatus, a blend tank, astorage apparatus and the like. The cooling apparatus for stopping theprogress of ripening may be constituted by a heat exchange system usinga plate type heat exchanger or the like, or by a vacuum cooling systemfor effecting cooling by utilizing latent heat of vaporization.

[0036] In this batch type production system, in order to perform theproduction process of the silver halide emulsion in one or pluralstages, the tank 10 as the batch type reaction container device equippedwith the agitator is used, and a plurality of chemicals in large amountsintroduced into the tank 10 for producing an emulsion are forcibly mixedby a magnetic agitation means 16.

[0037] The tank 10 as the batch type reaction container device equippedwith the agitator is suitable for production of a large quantity ofemulsion. However, when another new liquid chemical is injected throughthe emulsion introduction pipe 22 to the chemicals for producing theemulsion stored in the tank 10, and a plurality of chemicals in a largeamount introduced into the tank 10 are agitated by the agitation vane 12and are mixed, the liquid chemicals newly injected through the emulsionintroduction pipe 22 are stagnant in the vicinity of the injection portof the emulsion introduction pipe 22 or circulates in the tank 10.

[0038] Accordingly, in the initial state where a plurality of liquidchemicals in a large quantity for producing the emulsion are agitated bythe agitation vane 12 to start mixing thereof, it is inevitable such astate that the liquid chemical newly injected through the injection portof the emulsion introduction pipe 22 is locally mixed at a highconcentration into a part of the liquid chemicals for producing theemulsion stored in the tank 10 existing at a place where the chemicalsare circulated in the tank 10, and a mixing concentration of the liquidchemicals becomes low at a portion which is remote from the injectionport of the emulsion introduction pipe 22 and which the newly injectedliquid chemical does not reach through the circulation by the agitationvane 12.

[0039] Accordingly, when a plurality of liquid chemicals in a largeamount for producing an emulsion are stirred by the agitation vane 12, adifference in history of a chemical change arises between one wheremixing of the newly injected liquid chemical is started at a highconcentration thereof and one where mixing of the newly injected liquidagent is started at a low concentration thereof, so that the compoundsformed become non-uniform in the entire tank 10.

[0040] Further, a non-uniform chemical reaction may occur due to a deadspace existing in a small part in the tank 10, or due to variation inthe liquid flow when the liquid chemicals for producing the emulsion isstirred by the agitation vane 12.

[0041] In addition, when the liquid chemicals in a large quantity forproducing an emulsion in the tank 10 are heated by the temperaturecontrol means 18, since the temperature control means 18 heats thechemicals through the wall of the tank 10, there is a case where when aheating process is started, the liquid chemicals for producing theemulsion in the tank 10 are rapidly heated only at the place close tothe wall of the tank 10, and the temperature is not raised at the centerin the tank 10, so that the temperature distribution of the liquidchemicals for producing the emulsion in the tank 10 becomes uneven, ahistory difference in the chemical change, and compounds formed becomesnon-uniform in the entire tank 10.

[0042] Furthermore, in the method of forming silver halide grainsconstituting the silver halide emulsion, which is industrially carriedout today, there is a process in which a silver nitrate solution and ahalide solution are added to a dispersion medium solution (protectivecolloid solution) typified by gelatin under vigorous agitation, and aremixed as quickly as possible to form silver halide grains.

[0043] In this silver halide grain forming process, since an ionicreaction in which a silver ion and a halogen ion react with each otherto form silver halide is very rapid, it is essential to quickly agitateand mix these two ionic solutions in a short time in order to perform auniform reaction.

[0044] Here, for example, in the case where nucleus formation isperformed by a method in which a silver salt solution and a halidesolution are added to a dispersion medium in the tank 10 from theemulsion introduction pipe 22 and are agitated by the agitation vane 12,a vortex is generated by the agitation vane 12 rotating at a high speedin the liquid chemicals for producing the emulsion in which the silversalt solution and the halide solution are added in the dispersion mediumin the tank 10, and mixing by turbulent flow is carried out in theprocess in which the vortex is subdivided.

[0045] Even in this case, once the nuclei thus formed circulate in thetank 10 to cause a so-called local recycling, and at the same time asthe formation of the nuclei, crystal growth from the nuclei occurs inparallel, so that it is difficult to form mono dispersed nuclei.

[0046] Further, in the field of silver halide photography, a tabularsilver halide grain having a large light receiving area is widely usedas a photosensitive element. In order to increase a light receivingefficiency, a thin tabular silver halide grain is preferable.

[0047] However, in the batch type production system using the tank 10and the agitation vane 12 mentioned above, when the agitation isperformed by the agitation vane 12 to produce the silver halideemulsion, the tabular silver halide grains during the process of crystalgrowth pass through a high supersaturation region in the vicinity of theinjection port of the emulsion introduction pipe 22 for adding silverion or halide ion, and an adverse effect such that the thickness of thetabular grains increases is apt to occur.

[0048] Furthermore, in the batch type production system using the tank10 and the agitation vane 12, on the assumption that the quantity ofsilver halide emulsion produced at one time in the tank 10 is apredetermined constant quantity, the shape of the agitation vane 12 isdetermined to obtain an appropriate agitating state in the tank 10.Accordingly, when a production scale is changed to produce a desiredquantity of emulsion, there is a fear that the characteristics of theemulsion are changed, and the preparation scale cannot be changed.Therefore, a predetermined quantity of silver halide emulsion largerthan a desired quantity of emulsion must be produced, and as a result,there is a drawback that the silver halide emulsion produced in anexcess amount is wastefully discarded.

[0049] On the other hand, with respect to a newly prescribed silverhalide emulsion developed by using an experimental apparatus, in thecase where a small production system using the experimental apparatus isscaled up to a mass production system using a mass production apparatus,it is necessary to repeat trial production and product test many timesin order to verify conditions under which the same characteristics asthe emulsion characteristics obtained by the experimental apparatus forsmall production can be achieved in the newly prescribed silver halideemulsion produced by the production apparatus for mass production.Accordingly, there are problems that it takes a long time to develop theproduction system for mass production, and the loss of raw materialconsumed for the product test is large.

[0050] Furthermore, it has been proposed that a microreactor is used fora part of a production process of silver halide photographic emulsionused for photosensitive material (see, for example, Japanese PatentApplication No. 2001-76564).

[0051] The microreactor used in this method is one of micro devices, inwhich a plurality of solutions introduce into each mixing space throughmicrochannels having an equivalent diameter of several μm to severalhundred μm having a cross-section when converted into a circle, to causea chemical reaction.

[0052] In such a microreactor, two kinds of solutions are made to flowthrough fine liquid supply passages called microchannels and aresupplied as very thin lamella-like laminar flows into the mixing space,so that the two kinds of solutions are mixed and are allowed to reactwith each other in the mixing space (see, for example, JP-W No.9-512742, WIPO International Publication WO 00/62913).

[0053] In a fluid circuit used in such a microreactor, there is a casewhere it is required that three or more kinds of fluids are allowed torapidly react with one another by the microreactor. However, theconventional microreactor is constituted such that two kinds of fluidsare allowed to react with each other. Thus, in the case where three ormore kinds of fluids are made to react with each other by theconventional microreactor, it is necessary that a fluid circuit isconstituted such that two or more microreactors are connected in seriesby piping or the like, and three or more kinds of fluids are made toreact with each other step wisely by using this fluid circuit.

[0054] In such a fluid circuit, there is a limit in shortening adistance between a microreactor disposed at the upstream side and amicroreactor disposed at the downstream side, a certain period of timeis necessary to mix another fluid with two kinds of fluids in a reactioncontainer to make to react with the fluids each other. Therefore, it isimpossible to make to react with three kinds of fluids one another atthe same time. Moreover, in the fluid circuit, as the kinds of fluids tobe supplied are increased, the number of elements (microreactors)constituting the circuit is increased, so that the circuit structurebecomes complicated. Incidentally, this applies in the case where threeor more kinds of fluids are mixed at the same time.

[0055] In addition, in the conventional microreactor, plural liquidsupply passages respectively-have liquid supply ports facing a mixingspace so as to open respective liquid supply openings, and solutions areintroduced into the mixing space through these plural liquid supplyports. However, there exists a portion where the cross-section of themixing space is abruptly enlarged with respect to the sum of the openingareas of these liquid supply ports, and there exists a portion in themixing space where the direction of flow of solutions to be mixed isabruptly changed. The solutions are apt to stagnate in the vicinity ofthe portion where the cross-section is abruptly enlarged in this mixingspace or in the vicinity of the portion where the direction of the flowof the solutions to be mixed is abruptly changed, and especially in thecase where a reaction between solutions is a precipitation generationreaction accompanied by coalescence or growth, aggregation or depositionoccurs in the stagnant part, and there is a fear that there occursclogging due to this, or reduction of uniformity of a reaction productdue to the mixture of aggregates or deposits.

[0056] Further, in the conventional microreactor, according to the kindsof solutions supplied to plural liquid supply passages, a time whenthese solutions are mixed or a time when the mixing of the solutionsaccompanying a chemical reaction is performed, (hereinafter referred toas “mixing time”) is changed. That is, as the viscosity of the solutionbecomes high, the mixing time becomes longer in general, and in the casewhere the aggregation or deposition occurs accompanying the chemicalreaction between the solutions, the aggregates or deposits become aninhibiting factor of mixing, that is, causes the lowering of diffusingpower to the solution, and the mixing time is changed.

[0057] In such a microreactor, since the passage length in the flowdirection of the solutions in the mixing space is constant, in the casewhere the flow rate of the solutions is constant, a time (passing time)when the solutions pass through the mixing space becomes constant.Accordingly, in the case where the mixing time of the solutions in themixing space is longer than the passing time, it is necessary to reducethe flow rate of the solutions in the mixing space, so that theprocessing rate of the solutions in the microreactor is lowered. At thistime, in order to prevent the decrease in the process rate of thesolution, it is conceivable to extend the passage length of the mixingspace. However, in the case where such measures are taken, themicroreactor is enlarged or the production cost is increased. Further,in the case where the passage length of the mixing space is extendedmore than needs, the aggregation, deposition or the like of the solutionis promoted by contraries, the clogging occurs in the mixing space, andthe maintenance of the microreactor becomes troublesome.

[0058] Accordingly, in the foregoing conventional microreactor, anactuator is coupled to a block-shaped mixer element in which liquidsupply passages branching from a supply part of a solution in the shapeof the teeth of a comb are formed, a mechanical vibration is given tothe mixer element by this actuator, and the mixing of plural solutionsis accelerated by this mechanical vibration.

[0059] However, in this conventional microreactor, the vibration isgiven to only the mixer element in which plural liquid supply passagesare formed, and this vibration is transmitted to the solutions in themixing space through the solutions in the liquid supply passages, sothat the mixing of the solutions in the mixing space is accelerated.Thus, in such a microreactor, it is difficult to control the progress ofthe mixing of the solutions in the mixing space and the progress of thechemical reaction accompanying the mixing with high accuracy. Forexample, in the case where the chemical reaction between the solutionsin the mixing space is desired to be performed stepwise, or in the casewhere the solution and reaction product are desired to be diffused andmixed over the whole length of the mixing space, it is difficult torealize such progress of the mixing or the chemical reaction.

SUMMARY OF THE INVENTION

[0060] In view of the above facts, in the present invention, disturbancefactors, such as a deviation of a mixing state of liquid chemicalscaused due to liquid chemicals in a large quantity for producing anemulsion stirred and mixed by a turbulent flow, a deviation of arecycling flow state, or a deviation of a temperature distribution, areeliminated, and while a uniform chemical reaction in liquid chemicalsfor producing an emulsion is accelerated, a difference in history ofchemical change is made not to occur, and all produced compounds aremade to have a uniform emulsion property. Alternatively, the inventionhas an object to provide a production method of silver halidephotographic emulsion and a production apparatus of the emulsion, inwhich a small production system by an experimental apparatus can beeasily scaled up to a production apparatus for mass production, and theemulsion production is enabled at an optimum production scalecorresponding to a required production quantity.

[0061] According to a first aspect of the invention, a production methodof silver halide photographic emulsion comprises a nucleus formingprocess, a nucleus growing process, a chemical sensitizing process, anda spectral sensitizing process, wherein at least one of the nucleusforming process, the nucleus growing process, the chemical sensitizingprocess, and the spectral sensitizing process is performed by using amicroreactor.

[0062] By the constitution as described above, when viewedmicroscopically, the nucleus forming process for bonding a single silverion and a single halogen ion in one-to-one correspondence is carried outby using a minute region of the microreactor, and a reaction for formingdesired nuclei can be accurately carried out, or, nuclei of silverhalide newly supplied to grow grains (host grains) of nuclei of silverhalide formed by the nucleus forming process are made to uniformly meetthe grains (host grains) of the nuclei of silver halide to allow toreact with each other, conditions from the meeting of the grains (hostgrains) of the nuclei of silver halide and the nuclei of newly suppliedsilver halide at the same timing to the end of the reactions are madeuniform, and the grains (host grains) of the nuclei of silver halide canbe uniformly grown. Alternatively, each crystal lattice in the singlenucleus of silver halide is accurately doped with a predetermined number(for example, one molecule for each crystal lattice) of molecules forchemical sensitization, and the sensitizing process is performed, sothat it is possible to prevent a crystal lattice which is not doped withthe molecule for chemical sensitization from being formed, to prevent acrystal lattice which is excessively doped with the molecule forchemical sensitization from being formed, or to prevent a molecule forchemical sensitization from being in excess, and it is possible toprevent the agent for chemical sensitization from wasting.Alternatively, the spectral sensitizing process is performed in whichone layer of molecules of a spectral sensitizing agent is uniformlyadsorbed on the surface of the single nucleus (grain) of silver halide,so that it is possible to prevent the generation of a nucleus (grain) ofsilver halide on which the molecule for spectral sensitization is notadsorbed, to prevent the generation of a nucleus (grain) of silverhalide in an adsorption state in which molecules for spectralsensitization are excessive (multi-molecule adsorption state in whichmulti-layer molecules of the spectral sensitizing agent are adsorbed bythe surface of the nucleus (grain) of silver halide), or to prevent themolecule for spectral sensitization from being in excess, and it ispossible to prevent the agent for spectral sensitization from wasting.

[0063] As stated above, a silver halide photographic emulsion havinguniform emulsion characteristics can be produced by using themicroreactor. Further, since the microreactor is used, a smallproduction system can be easily scaled up to a mass production system,and the emulsion can be produced at an optimum production scalecorresponding to a required production quantity.

[0064] According to a second aspect of the invention, a productionmethod of silver halide photographic emulsion comprises a nucleusforming process, a nucleus growing process, a chemical sensitizingprocess, and a spectral sensitizing process, wherein, when at least oneof the nucleus forming process, the nucleus growing process, thechemical sensitizing process, and the spectral sensitizing process iscarried out, temperature control of a process liquid is executed byusing a microreactor including a temperature control means forcontrolling the temperature of the process liquid.

[0065] By the constitution as described above, in the case where thetemperature control is executed by introducing the process liquid intothe microreactor having the temperature control means for controllingthe temperatures of the process liquids to perform heat transfer, thethermal energy is transmitted in a state where the process liquid formsa thin layer and the quantity thereof is very small, so that temperaturechanges rapidly to an objective set temperature. Thus, in the case wherethe temperature control is executed by the microreactor having thetemperature control means for controlling the temperature of the processliquids, since it can be said that the timing of temperature change doesnot deviate between infinitesimal liquid chemicals for producing anemulsion forming thin layers, it is possible to prevent occurrence ofdifference in the liquid chemicals for producing the emulsion due to thedifference in the history of the temperature change. Further, in thecase where the temperature control is executed by the microreactorhaving the temperature control means for controlling the temperature ofthe process liquid, thermal energy is transferred to the infinitesimalliquid chemicals for producing an emulsion which form very thin layersand flow within the microreactor having the temperature control meansfor controlling the temperature of the process liquids, so that thetemperature change of the liquid chemicals for producing the emulsion iscompleted.

[0066] Thus, in the case where the temperature control is executed bythe microreactor having the temperature control means for controllingthe temperature of the process liquids, a waiting time from the start ofthe temperature change of the liquid chemicals for producing theemulsion to the completion is eliminated, and the whole process time canbe greatly shortened. In addition, in the case where the temperaturecontrol is executed by the microreactor having the temperature controlmeans for controlling the temperature the process liquids, the rate ofthe temperature change of the liquid chemicals for producing theemulsion is high (good responsiveness to the temperature change), andthere is no stagnancy and no recycling flow, so that the controloperation of the temperature of the liquid chemicals for producing theemulsion can be precisely controlled, and an appropriate silver halidephotographic emulsion can be produced.

[0067] In addition, since the microreactor is used, a small productionsystem can be easily scaled up to a mass production system, and theemulsion can be manufactured at an optimum production scale inaccordance with a required production quantity.

[0068] According to a third aspect of the invention, a productionapparatus of silver halide photographic emulsion, which performs anucleus forming process, a nucleus growing process, a chemicalsensitizing process or a spectral sensitizing process, comprises: afirst liquid guiding pipe which collects process liquids processed byusing plural microreactors for performing the nucleus forming process,and thereafter feeds the liquids to a next process; a second liquidguiding pipe which is connected to the first liquid guiding pipe fordistributing and supplying the process liquids to plural microreactorswhich has a processing capacity equivalent to all of the processingcapacities of the plural microreactors for performing the nucleusforming process for performing the nucleus growing process; a thirdliquid guiding pipe which collects the process liquids processed byusing the plural microreactors for performing the nucleus growingprocess, and thereafter feeds the process liquids to a next process; anda fourth liquid guiding pipe for distributing and supplying the processliquids for the chemical sensitizing process or the spectral sensitizingprocess to plural microreactors.

[0069] By the constitution as described above, when each of the nucleusforming process, the nucleus growing process, the chemical sensitizingprocess and the spectral sensitizing process is ended and started, thecollection and distribution of the process liquids are repeated, so thatthe liquid chemicals for producing the emulsion processed in therespective microreactors are mutually mixed to be uniform at the endpoint of each process, and the quality and performance of the finallyproduced silver halide photographic emulsion can be made uniform.

[0070] In the production apparatus of the silver halide photographicemulsion constituted in this series of lines, the number ofpredetermined plural microreactors installed at each process is suitablyset in accordance with the processing capacity or the like, so that theflow rate of the liquid chemicals for producing the emulsion between therespective processes becomes constant, and the whole production systemcan be constituted such that the process liquids do not stagnate and theprocess can be efficiently performed.

[0071] As stated above, the silver halide photographic emulsion havinguniform emulsion performance can be produced by the microreactors.

[0072] A fourth aspect of the present invention is a productionapparatus of silver halide photographic emulsion, which performs anucleus forming process by using plural microreactors, performs anucleus growing process by using plural microreactors, and performs achemical sensitizing process or a spectral sensitizing process by usingplural microreactors, wherein process liquids which have been forwardedto a next process from the plural microreactors for performing at leastone process of the plural microreactors for carrying out the nucleusforming process, the plural microreactors for carrying out the nucleusgrowing process, the plural microreactors for carrying out the chemicalsensitizing process, and the plural microreactors for carrying out thespectral sensitizing process are collected and are temporarily stored ina storage tank, and the process liquids are distributed and supplied tothe plural microreactors from the storage tank for performing the nextprocess.

[0073] By the constitution as described above, it is possible to proceedwith the operation in such a way that the process liquids aretemporarily stored in the storage tank at the point of time when thenucleus forming process, the nucleus growing process, the chemicalsensitizing process, or the spectral sensitizing process in theproduction process of the silver halide photographic emulsion isperformed, and thereafter, a subsequent process is carried out at asuitable point of time of the operation. Further, the process liquidsprocessed by the plural microreactors provided in parallel arerespectively collected in the storage tank, are blended and can be used.Therefore, the process liquids having the same characteristics, whichhave been respectively collected in the storage tanks, are mixed,distributed and supplied to the plural microreactors provided inparallel, so that the uniform silver halide photographic emulsion can beproduced.

[0074] In addition, since the microreactors are used, a small productionsystem can be easily scaled up to a mass production system, and theemulsion can be manufactured at an optimum production scalecorresponding to a required production quantity.

BRIEF DESCRIPTION OF THE DRAWINGS

[0075]FIG. 1 is a schematic structural explanatory diagram showing thewhole of a single line production apparatus of silver halidephotographic emulsion according to a first embodiment of the presentinvention.

[0076]FIG. 2 is a schematic explanatory diagram showing the processcontents of respective production processes in the single lineproduction apparatus of the silver halide photographic emulsionaccording to the first embodiment of the invention.

[0077]FIG. 3 is a schematic structural explanatory diagram showing thewhole of a production apparatus of silver halide photographic emulsionof a first structural example according to a second embodiment of theinvention.

[0078]FIG. 4 is a schematic structural explanatory diagram showing thewhole of a production apparatus of silver halide photographic emulsionof a second structural example according to the second embodiment of theinvention.

[0079]FIG. 5 is a schematic structural explanatory diagram showing thewhole of a production apparatus of silver halide photographic emulsionof a third structural example according to the second embodiment of theinvention.

[0080]FIG. 6 is a schematic structural explanatory diagram showing astructural example of a nucleus forming reaction microreactor for mixingtwo liquids and a nucleus growing reaction controlling microreactor in asilver halide photographic emulsion production apparatus according to athird embodiment of the invention.

[0081]FIG. 7 is a schematic structural explanatory diagram showing astructural example of a nucleus forming reaction microreactor for mixingthree liquids and a nucleus growing reaction-controlling microreactor inthe silver halide photographic emulsion production apparatus accordingto the third embodiment of the invention.

[0082]FIG. 8 is a schematic structural explanatory diagram showing astructural example of a pre-processing microreactor for mixing twoliquids and a nucleus forming reaction microreactor for mixing twoliquids in the production apparatus of the silver halide photographicemulsion according to the third embodiment of the invention.

[0083]FIG. 9 is a schematic structural explanatory diagram showing astructure in which a nucleus forming process microreactor and a mixerare provided in a sidearm emulsion preparation for performing a nucleusforming process in the grain formation of silver halide emulsion at apre-ripening process according to a fourth embodiment of the invention.

[0084]FIG. 10 is a schematic structural explanatory diagram showing amicroreactor for a nucleus forming reaction and physical ripeningreaction, which performs a nucleus forming process and initiates thesubsequent a nucleus growing process in the grain forming process ofsilver halide emulsion in a pre-ripening process according to a fifthembodiment of the invention.

[0085]FIG. 11 is a schematic structural diagram showing a nucleusforming reaction and physical ripening reaction microreactor and a microheat exchanger, in which a nucleus forming process in the grain formingprocess of silver halide emulsion is performed, nucleus growth istemporarily stopped at the stage when desired nuclei are formed so as tolead to the subsequent grain growing reaction in the pre-ripeningprocess according to the fifth embodiment of the invention.

[0086]FIG. 12 is a schematic structural diagram showing a nucleusforming reaction and physical ripening reaction microreactor, a microheat exchanger, and a nucleus growing microreactor, in which a nucleusforming process in the grain forming of silver halide emulsion isperformed, nucleus growth is temporarily stopped at a stage when desirednuclei are formed to continue the subsequent physical ripening reactionin the pre-ripening process of the fifth embodiment of the invention.

[0087]FIGS. 13A, 13B, 13C, 13D and 13E are perspective viewsexemplifying crystal structures of nuclei when the nucleus formation isperformed by the production method and the production apparatus for asilver halide photographic emulsion of the invention.

[0088]FIG. 14 is a schematic structural view showing a spectralsensitizing processing microreactor for performing a spectralsensitizing process of the silver halide photographic emulsion in anafter-ripening process of a production method and a silver halidephotographic emulsion production apparatus according to a sixthembodiment of the invention.

[0089]FIG. 15 is a schematic view showing a reaction tank apparatus forperforming a nucleus forming process in the grain forming process of asilver halide emulsion in a pre-ripening process using a silver halidephotographic emulsion production apparatus according to a seventhembodiment of the invention.

[0090]FIG. 16 is a plan view showing a two-liquid mixing microreactorchip for performing the nucleus forming process in the grain formingprocess of the silver halide emulsion in the pre-ripening process usingthe silver halide photographic emulsion production apparatus accordingto the seventh embodiment of the invention.

[0091]FIG. 17 is a plan view showing a two-liquid mixing microreactorchip constituted to be capable of enhancing the process capacity, forperforming the nucleus forming process in the grain forming process ofthe silver halide emulsion in the pre-ripening process using the silverhalide photographic emulsion production apparatus according to theseventh embodiment of the invention.

[0092]FIG. 18 is a plan view showing a three-liquid mixing microreactorchip for performing the nucleus forming process in the grain formingprocess of the silver halide emulsion in the pre-ripening process usingthe silver halide photographic emulsion production apparatus accordingto the seventh embodiment of the invention.

[0093]FIG. 19 is a schematic explanatory view showing the processcontent in another production process in a production apparatus ofsilver halide photographic emulsion of the invention.

[0094]FIG. 20 is an exploded perspective view showing the main part of amixing microreactor device that can be used for a silver halidephotographic emulsion production apparatus of the invention.

[0095]FIG. 21 is an exploded perspective view showing the main part of amulti function microreactor device that can be used for a silver halidephotographic emulsion production apparatus of the invention.

[0096]FIGS. 22A and 22C are plan views showing a structure of an exampleof a microreameor according to No. 1 of an eighth embodiment of theinvention, and FIG. 22B is a side cross-sectional view showing thestructure of the example of the microreactor according to No. 1 of theeighth embodiment of the invention.

[0097]FIG. 23 is an exploded perspective view of the microreactor shownin FIG. 22.

[0098]FIGS. 24A and 24D are plan views showing a structure of a baseplate in the microreactor shown in FIG. 22, and FIGS. 24B and 24C areside cross-sectional views thereof.

[0099]FIG. 25 is a perspective view showing a back surface part of thebase plate in the microreactor shown in FIG. 22.

[0100]FIG. 26 is a side cross-sectional view schematically showing thestructure of the microreactor shown in FIG. 22, and shows the flows ofsolutions before and after mixing thereof in the microreactor.

[0101]FIGS. 27A and 27C are plan views showing a structure of a modifiedexample of the microreactor according to No. 1 of the eighth embodimentof the invention, and FIG. 27B is a side cross-sectional view thereof.

[0102]FIGS. 28A and 28C are plan views showing a structure of a modifiedexample of the microreactor according to No. 1 of the eighth embodimentof the invention, and FIG. 28B is a side cross-sectional view thereof.

[0103]FIGS. 29A and 29C are plan views showing a structure of amicroreactor according to No. 2 of the eighth embodiment of theinvention, and FIG. 29B is a side cross-sectional view thereof.

[0104]FIGS. 30A is a cross-sectional view showing a structure of anexample of a microreactor according to No. 1 of a ninth embodiment ofthe invention in an axial direction, and FIG. 30B is a cross-sectionalview in a direction orthogonal to an axis.

[0105]FIG. 31A is a cross-sectional view showing a structure of amodified example of the microreactor according to No. 1 of the ninthembodiment of the invention in the axial direction, and FIG. 31B is across-sectional view in the direction orthogonal to the axis.

[0106]FIG. 32A is a cross-sectional view showing a structure of anothermodified example of the microreactor according to No. 1 of the ninthembodiment of the invention in the axial direction, and FIG. 32B is across-sectional view in the direction orthogonal to the axis.

[0107]FIG. 33A is a cross-sectional view showing a structure of anexample of a microreactor according to No. 2 of the ninth embodiment ofthe invention in an axial direction, and FIG. 33B is a cross-sectionalview in a direction orthogonal to an axis.

[0108]FIG. 34A is a cross-sectional view showing a structure of anexample of a microreactor according to No. 1 of a tenth embodiment ofthe invention in an axial direction, and FIG. 34B is a cross-sectionalview in a direction orthogonal to an axis.

[0109]FIG. 35A is a cross-sectional view showing a structure of amodified example of the microreactor according to No. 1 of the tenthembodiment of the invention in the axial direction, and FIG. 35B is across-sectional view in the direction orthogonal to the axis.

[0110]FIG. 36A is a cross-sectional view showing a structure of amicroreactor according to No. 2 of the tenth embodiment of the inventionin the axial direction, and FIG. 36B is a cross-sectional view in thedirection orthogonal to the axis.

[0111]FIG. 37 is a schematic structural diagram exemplifying aproduction apparatus of silver halide photographic emulsion according toa conventional batch type production system.

DETAILED DESCRIPTION OF THE INVENTION

[0112] Embodiments of a production apparatus of silver halidephotographic emulsion of the present invention will be described withreference to the accompanying drawings.

[0113]FIG. 1 is a whole schematic structural view showing a productionsystem according to a first embodiment in a production apparatus ofsilver halide photographic emulsion of the invention. The productionsystem of the first embodiment shown in FIG. 1 is constituted as asingle line production system in which a pre-ripening process (a nucleusforming process, a first crystal growing process, and a second crystalgrowing process), a desalting process and an after-ripening process aresuccessively performed.

[0114] Incidentally, the single line production system may beconstituted such that in these processes, two or more processes arecombined into one operation and are performed, one or more stages areomitted from the production processes, or plural operations are repeatedat each stage to obtain a desired emulsion.

[0115] The single line production system for producing the silver halidephotographic emulsion as shown in FIG. 1 is constituted such thatmicroreactors are used to perform the pre-ripening process (the nucleusforming process, the first crystal growing process, and the secondcrystal growing process) and the after-ripening process.

[0116] Here, the microreactor in the specification is defined such that“the microreactor has a three-dimensional structure used for performingmixing, or mixing and chemical reaction, and is formed on a solidsubstrate by a suitable process in the microtechnology, and themicroreactor normally introduces a fluid from a flow passage(microchannel) having an equivalent diameter of 500 μm or less per oneintroduction passage to a space where the mixing, or the mixing andchemical reaction are performed, and performs the mixing, or the mixingand the chemical reaction.”

[0117] Further, in the specification, as long as the construction is thesame, the microreactor includes a so-called micromixer (one having thefunction of mixing fluids). At the same time as this, it is presumedthat the term of the micromixer includes the microreactor, and themicroreactor and the micromixer are recognized to be the same.

[0118] Furthermore, in the specification, a heat exchange microreactoris defined such that “a heat exchange microreactor has athree-dimensional structure used for performing mixing, or mixing andchemical reaction, and is formed on a solid substrate by a suitableprocess in the microtechnology, and the heat exchange microreactornormally introduces a fluid from a flow passage (microchannel) having anequivalent diameter of 500 μm or less per one introduction passage to aspace where the mixing or the mixing and the chemical reaction areperformed, and performs the mixing, or the mixing and chemical reaction,and further, the heat exchange microreactor includes means forperforming a temperature control of fluid for the purpose of controllingthe mixing, or the mixing and chemical reaction.”

[0119] In addition, a micro heat exchanger in the specification isdefined such that “a micro heat exchanger is a three-dimensionalstructure used for performing a temperature control of fluid, and isformed on a solid substrate by a suitable process in themicrotechnology, and the micro heat exchanger normally includes a flowpassage (microchannel) having an equivalent diameter of 500 μm or lessper one introduction passage, and includes means for performing atemperature control of fluid flowing through this flow passage.”

[0120] As shown in FIG. 1, in the single line production system forproducing a silver halide photographic emulsion, a nucleus formingprocess in a pre-ripening process is performed by a microreactor A30.

[0121] This microreactor A30 is constituted as a microreactor forsimultaneously mixing three liquids. A silver nitrate solution, anaqueous protective colloid solution, and a halide solution aresimultaneously mixed by this microreactor A30, and a nucleus formingprocess for forming microcrystalline dispersion of silver halide in theaqueous protective colloid solution is performed.

[0122] In the case where the nucleus forming process is performed byusing this microreactor A30, when viewed microscopically, a singlesilver ion and a single halogen ion are bonded to each other inone-to-one correspondence. Heat generated at this time is absorbed so asto suppress and control Ostwald ripening, so that a reaction of suitablyforming desired nuclei can be stably performed.

[0123] This microreactor A30 is constituted to be automaticallycontrolled by a control device on the basis of a detection valuedetected by an unillustrated detection sensor. Incidentally, in theautomatic control for the microreactor A30 by this control device, apotential control means for a nucleus forming process or a means forcontrolling a nucleus forming process by detecting a physical quantitysuch as a pH value, which have conventionally been used, may be used.

[0124] A nucleus 40 that is a microcrystal of silver halide asexemplified in FIG. 2 is formed in this nucleus forming process, and theprocess proceeds to the subsequent first crystal growing process in thepre-ripening process.

[0125] In the first crystal growing process, the liquid chemicals forproducing the emulsion, in which the silver halide microcrystals aredispersed in the aqueous protective colloid solution, which are sentfrom the microreactor A30, are introduced into a heat exchangemicroreactor A32 as a microreactor including a temperature control meansfor controlling the temperature of a process liquid, and temperaturecontrol and physical ripening are performed so that the liquid chemicalsfor producing the emulsion are brought to a predetermined temperaturesuitable for nucleus growth at the first crystal growing process. Thisheat exchange microreactor A32 executes the temperature control bymaking a heat exchange between the liquid chemicals for producing theemulsion introduced into the microreactor 32 and atemperature-controlling medium.

[0126] In the case where the liquid chemicals for producing theemulsion, in which the nuclei of silver halide are dispersed in theaqueous protective colloid solution, are introduced into the heatexchange microreactor A32, and the temperature control is executed bymaking the heat exchange of the liquid chemicals with thetemperature-controlling medium. Since heat energy is transferred in aninfinitesimal state where the liquid chemicals for producing theemulsion form a thin layer, the temperature of the liquid chemicalschanges rapidly to an objective set temperature.

[0127] Thus, in the case where the temperature control is executed bythe heat exchange microreactor A32, since it can be said that the timingof temperature change does not deviate between the infinitesimal liquidchemicals for producing an emulsion forming the thin layers, occurrenceof differences in produced chemical substances due to differences inhistory of temperature changes can be prevented.

[0128] Further, in the case where the temperature control is executed bythe heat exchange microreactor A32, heat energy is exchanged with theinfinitesimal liquid chemicals for producing an emulsion which form thinlayers and flow in the inside of the heat exchange microreactor A32, andthe temperature change of the liquid chemicals for producing theemulsion is completed.

[0129] Thus, in the case where the temperature control is executed bythe heat exchange microreactor A32, it is possible to eliminate awaiting time from the start of the temperature change of the liquidchemicals for producing the emulsion to the completion of the heatchange. For example, when a large quantity of liquid chemicals forproducing an emulsion stored in a large tank is heated through the outerperipheral wall of the tank, it takes a long waiting time (waiting timeof a time order) for the large quantity of liquid chemicals forproducing an emulsion in the large tank to change to a predeterminedtemperature. On the other hand, in the case where the temperaturecontrol is executed by the heat exchange microreactor A32, this longwaiting time (loss time) can be eliminated, so that the process time canbe greatly shortened.

[0130] In addition, in the case where the temperature control isexecuted by the heat exchange microreactor A32, the rate of thetemperature change of the liquid chemicals for producing the emulsion ishigh (good responsiveness to the temperature change), and there is nostagnant flow and no recycling flow, so that the control operation oftemperature of the liquid chemicals for producing the emulsion can beprecisely controlled, and it is suitably used for a case wheretemperature is a dominant factor of a chemical change.

[0131] At this time, the nucleus 40 of the silver halide microcrystalexemplified in FIG. 2 grows into a nucleus 42 of a small crystal ofsilver halide.

[0132] The liquid chemicals for producing the emulsion containing thenucleus 42 of the small crystal of silver halide, as a so-called hostgrain, which have been subjected to a temperature control and physicalripening at a predetermined temperature by the heat exchangemicroreactor A32, are introduced into a microreactor B34, and aresimultaneously mixed with an additional silver nitrate solution andhalide solution to accelerate an Ostwald ripening. The nucleus 42 of thesmall crystal of silver halide as exemplified in FIG. 2 grows into thenucleus 44 of a medium-sized crystal of silver halide, and the processproceeds to the next second crystal growing process in the pre-ripeningprocess.

[0133] In the second crystal growing process, the liquid chemicals forproducing the emulsion in which the nuclei 44 of the medium-sizedcrystal of silver halide are dispersed in the aqueous protective colloidsolution, which have been sent from the microreactor B34 are introducedinto an unillustrated heat exchange microreactor as the need arises. Thetemperature control is performed so that the liquid chemicals forproducing the emulsion have a predetermined temperature suitable for thegrowth of the nuclei in the second crystal growing process, and theliquid chemicals are introduced into a microreactor C36.

[0134] This microreactor C36 is constituted as a micromixer forsimultaneously mixing two liquids. In this two-liquid mixingmicroreactor C36, the liquid chemicals for producing the emulsion inwhich the nuclei 44 of the medium-sized crystals of silver halide aredispersed in the aqueous protective colloid solution and the aqueousprotective colloid solution containing the nuclei 40 of themicrocrystals of silver halide formed by the microreactor D38 aresimultaneously mixed to further promote the Ostwald ripening, and thenuclei 40 of the microcrystals of silver halide are consumed, so thatthe nuclei 44 of the middle crystal of silver halide as exemplified inFIG. 2 are made to grow into a nuclei 46 of large crystals of silverhalide.

[0135] At this time, in the microreactor C36, in the liquid chemicalsfor producing the emulsion in which the nuclei 44 (host grains) of themedium-sized crystals of silver halide are dispersed in the aqueousprotective colloid solution, nuclei of silver halide formed by themicroreactor D38 which are to be newly supplied to grow the grains (hostgrains) of the nuclei 44 of silver halide are made to uniformly meet thegrains (host grains) of silver halide in the inside of minute channelsin the microreactor C36 to cause the Ostwald ripening reaction, andconditions from the meeting of the grains (host grains) of the nuclei ofsilver halide and the newly supplied nuclei of silver halide at the sametiming to the end of the reaction are made uniform, and the respectivegrains (host grains) of the nuclei of silver halide can be made touniformly grow.

[0136] This microreactor D38 is constituted similarly to the foregoingmicroreactor A30, and is constituted as a micromixer for simultaneouslymixing three liquids, in which a silver nitrate solution, an aqueousprotective colloid solution and a halide solution are simultaneouslymixed to effect a nucleus forming process for forming a microcrystaldispersion of silver halide in the aqueous protective colloid solution,and the aqueous protective colloid solution containing the nuclei 40 ofthe microcrystals of silver halide thus formed is supplied to themicroreactor C36.

[0137] The liquid chemicals for producing the emulsion which the secondcrystal growing process in the pre-ripening process has been completedand in which the nuclei 46 of the large crystals of silver halide aredispersed in the aqueous protective colloid solution as stated above,are sent from the microreactor C36 to a desalting device 48 of thesubsequent desalting process.

[0138] In the desalting device 48, by using flocculation method, anoodle method, an ultrafiltration method, or an electro dialysis method,which is generally used, a process of removing unnecessary substancesformed during the emulsion grain formation in the pre-ripening process,excessively existing ions, and the like from the liquid chemicals forproducing the emulsion is carried out. Incidentally, the desaltingprocess may be performed by a microreactor constituted such that theunnecessary substances and the excessively existing ions can beseparated.

[0139] The liquid chemicals for producing the emulsion in which thedesalting process have been completed in the desalting device 48 and thenuclei 46 of the large crystal of silver halide are dispersed in theaqueous protective colloid solution, are sent to an after-ripeningprocess.

[0140] In the after-ripening process, the liquid chemicals for producingthe emulsion which are sent from the desalting device 48 and in whichthe nuclei 46 of the large crystals of silver halide are dispersed inthe aqueous protective colloid solution is introduced into anunillustrated heat exchange microreactor as the need arises. Atemperature control is performed so that the liquid chemicals forproducing the emulsion in which the nuclei 46 of the large crystals ofsilver halide are dispersed have a predetermined temperature suitablefor a chemical sensitizing process for increasing the sensitivitythereof to a high sensitivity of a practical level, and subsequently,the liquid chemicals are introduced into a microreactor A50 foraddition.

[0141] This microreactor A50 for addition is constituted as amicroreactor for simultaneously mixing two liquids. In the microreactorA50 for addition, the liquid chemicals for producing the emulsion inwhich the nuclei 46 of the large crystal of silver halide are dispersedin the aqueous protective colloid solution, and a chemical sensitizingagent are simultaneously mixed, the nuclei 46 of the large crystals ofsilver halide are subjected to the sensitizing process to formchemically sensitized nuclei 52 of silver halide as shown in FIG. 2.

[0142] In the chemical sensitizing process, a sulfur sensitizingprocess, gold sensitizing process, or reduction sensitizing process iscarried out which has been conventionally used. When the chemicalsensitizing process is carried out by doping the nuclei 46 of silverhalide with the chemical sensitizing agent by using the microreactor A50for addition, when viewed microscopically, since a predeterminedquantity (for example, one molecule for each crystal lattice) ofmolecule for chemical sensitization can be accurately doped in therespective crystal lattices in the single nucleus 46 of silver halide,the suitable chemical sensitizing process can be performed.

[0143] Thus, in the case where the chemical sensitizing process iseffected by using the microreactor A50 for addition, it is possible toprevent a crystal lattice which is not doped with the molecule forchemical sensitization from being formed, to prevent a crystal latticewhich is excessively doped with the molecules for chemical sensitizationfrom being formed, or to prevent a molecule for chemical sensitizationfrom being in excess, so that it is possible to prevent the agent forchemical sensitization from being wasted.

[0144] Further, in this after-ripening process, as shown in FIG. 2,subsequent to the chemical sensitizing process, by using anunillustrated microreactor for addition, spectral sensitizing processesare performed to widen the intrinsic photosensitive region of the liquidchemicals for producing the emulsion, in which the chemically sensitizednucleus 52 of silver halide are dispersed, to the respectivephotosensitive wavelength regions of blue, green, and red as the threeprimary colors of light, so that the spectrally sensitized nuclei 54 ofsilver halide are formed as shown in FIG. 2.

[0145] The spectral sensitizing process is a conventionally used processin which a solution containing a sensitizing dye dissolved in methanolis mixed and the sensitizing dye is adsorbed by the nuclei 52 of silverhalide.

[0146] In the case where the liquid chemicals for producing the emulsionin which the nuclei (grain) of silver halide are dispersed in theaqueous protective colloid solution are simultaneously mixed with thespectral sensitizing agent in which the spectral sensitizing dye isdissolved in methanol and the spectral sensitizing process is performedby using the microreactor for addition, when viewed microscopically,since a single layer of molecules of the spectral sensitizing agent canbe uniformly adsorbed by the surface of the single nucleus (grain) ofsilver halide, the suitable spectral sensitizing process can beeffected.

[0147] Thus, in the case where the microreactor for addition is used toeffect the spectral sensitizing process, it is possible to prevent theformation of nuclei (grain) of silver halide on which the molecule ofthe spectral sensitizer is not adsorbed, to prevent the formation ofnuclei (grain) of silver halide on which the molecules are excessivelyadsorbed (multi-molecule adsorbed state in which multi-layer moleculesof the spectral sensitizing agent are adsorbed on the surface of thenuclei (grain) of silver halide), or to prevent molecules for spectralsensitization from being in excess, so that it is possible to preventthe chemicals for spectral sensitization from being wasted.

[0148] In the solution of the silver halide photographic emulsionsubjected to the spectral sensitizing process, a stabilizing agent orthe like is added in the after-ripening process by using anunillustrated microreactor for addition to impart required propertiesthereto.

[0149] Incidentally, in the solution of the silver halide photographicemulsion, also in the case where the stabilizing agent or the like isadded by using an unillustrated mixing microreactor to impart therequired properties thereto, the same function and effect can beobtained.

[0150] After a temperature control is performed to attain apredetermined temperature suitable for storage, the thus produced silverhalide photographic emulsion is sent to a unillustrated storagecontainer and is refrigerated, and the series of production operationsof the silver halide photographic emulsion are completed.

[0151] The production apparatus of the silver halide photographicemulsion having a single line in series by using the aforementionedmicroreactors as shown in FIG. 1 constitutes an apparatus for so-calledfine chemicals, which is suitable for a case where a silver halidephotographic emulsion having uniform characteristics is continuouslyproduced little by little with a high reproducibility.

[0152] Thus, the production apparatus of the silver halide photographicemulsion using the microreactors is also suitable for an experimentalapparatus used when the combination of various agents for production ofsilver halide photographic emulsion is changed, and of emulsions areproduced in a small quantity and are evaluated to study formulationsduring the process in the development of a new silver halidephotographic emulsion in a laboratory.

[0153] In addition, the production apparatus of the silver halidephotographic emulsion having a single line in series by using themicroreactors shown in FIG. 1 may be constituted such that as shown inFIG. 19, a nucleus forming process is performed by another device (thedevice may not use a microreactor), liquid chemicals for producing anemulsion separately prepared in advance, in which the nuclei 42 of thesmall crystal of silver halide are dispersed in an aqueous protectivecolloid solution, are directly introduced into a microreactor B (notshown) for the first crystal growing process, and the operation proceedsto the subsequent second crystal growing process, desalting process, andafter-ripening process.

[0154] By the constitution as described above, since a fine nucleusforming process is performed by a specific apparatus and various nucleiare formed as desired and can be used, the degree of freedom concerninga method for producing the silver halide photographic emulsion can bewidened.

[0155] Further, the production apparatus of the silver halidephotographic emulsion constituted to have the single line in series byusing the microreactors according to the first embodiment may beconstituted such that at least one of the nucleus forming process, thefirst crystal growing process, the second crystal growing process, andthe after-ripening process is performed by a microreactor. That is, theproduction apparatus of the silver halide photographic emulsionaccording to the first embodiment may be constituted as a single lineproduction apparatus in series in which the microreactor and a batchtype reaction container device having an agitator and a temperaturecontrol means are used in combination.

[0156] Specific conditions of the production apparatus of the silverhalide photographic emulsion structured as the single line in seriesutilizing the microreactor, are exemplified below:

[0157] 1) flow rate range of liquid for use in each microreactor;

[0158] one or more micro liters per minute, preferably one or moremilliliters per minute;

[0159] 2) temperature range of liquid for in each microreactor;

[0160] from 5° C. to 95° C., preferably from 5° C. to 75° C.;

[0161] 3) throughput of the production apparatus of the silver halidephotographic emulsion constituted as a single line;

[0162] one or more micro liters per minute, preferably one or moremilliliters per minute, more preferably, ten or more milliliters perminute;

[0163] 4) connection method for a microreactor, a heat exchangemicroreactor, and a micro heat exchanger;

[0164] the respective microdevices may be disposed to be brought intodirect contact with each other without an interval, or the respectivemicrodevices may be disposed to be coupled by fixed pipes or removablepipes, and the pipe may be a pipe made of metal, ceramic, glass, resin,or composite material and may be firmly fixed or flexibly removable; and

[0165] 5) liquid feed method of liquid for use to a microreactor, a heatexchange microreactor, or a micro heat exchanger;

[0166] both a continuous flow type and a liquid droplet (liquid plug)type may be used, and as a driving force, both an electric drivingsystem and a pressure driving system may be used.

[0167] In the case of continuous production of silver halidephotographic emulsion, the pressure driving method of the continuousflow type is desirable. In that case, a commercially available normalpump may be used (for example, a syringe pump, a plunger pump or thelike may be used). Here, as a method of quantitatively feeding a liquidwithout pulsation, for example, means described in JP-A Nos. 62-182623,8-146543, 2001-109092, 2001-113219 and 2001-114397 can be used.

[0168] Next, chemical matters used in the production apparatus of thesilver halide photographic emulsion of the invention will be described.

[0169] The foregoing halide solution used in the invention is normally asolution of potassium bromide, sodium bromide, potassium chloride,sodium chloride, potassium iodide, sodium iodide, or a mixture thereof.

[0170] When a silver halide grain obtained by the method of theinvention is used as a nucleus, the concentration of the solution ispreferably 4 mol/L or less, more preferably 1 mol/L or less, and mostpreferably 0.2 mol/L or less. In the case where it is used for crystalgrowth, in view of the productivity, it is preferable to use a highlyconcentrated aqueous solution. The concentration is preferably from 0.5mol/L to 4 mol/L, and more preferably 1.0 mol/L or more. The temperatureof the aqueous solution is from 5° C. to 95° C., and preferably from 5°C. to 75° C.

[0171] It is preferable that gelatin is contained in at least one of asilver salt solution and a halide solution. Since the gelatin has agreat influence on a probability of formation of twin crystals in thegenerated silver halide grain, the preferable concentration of anaqueous gelatin solution varies with the objects of formed fine-grainsilver halide grain to be used.

[0172] In the case where continuously formed silver halide grains areused as nuclei at the time when a tabular silver halide grains areprepared, since parallel double twin crystal nuclei are required, it isnecessary to adjust the concentration of the aqueous gelatin solution soas to achieve a desired probability of twin crystal generation. It ispreferable to select the gelatin concentration so that when the aqueoussilver salt solution and the aqueous halide solution are mixed, thequantity of gelatin per 1 g of silver becomes from 0.03 g to 0.4 g, andmore preferably, 0.3 g or less.

[0173] In the case where continuously produced silver halide grains areused as nuclei at the time when normal crystal grains are prepared,since it is necessary to make a probability of formation of twincrystals as low as possible, it is necessary to raise the gelatinconcentration at the time of nucleus formation, and the quantity ofgelatin per 1 g of silver nitrate is 0.4 g or more (although there is noupper limit, preferably 50 g or less), preferably 1 g or more, and morepreferably 5 g or more.

[0174] The fine-grain silver halide emulsion obtained by this inventioncan be used at the time of crystal growth of the silver halide grain. Inthe case where it is used for the crystal growth, it is preferable thatadded silver halide fine grains are rapidly dissolved. For this purpose,it is preferable that the number of twin crystals is small, andtherefore, it is preferable that the concentration of an aqueous gelatinsolution is high. The concentration of the aqueous gelatin solution ispreferably made such a concentration that gelatin of from 0.2 g to 1 gis added per 1 g of silver nitrate, more preferably 0.3 g or more, andmost preferably 0.4 g or more.

[0175] In the case where the concentration of an aqueous gelatinsolution is made high, the viscosity of the aqueous gelatin solutionincreases, so that the addition of the aqueous gelatin solution becomesdifficult. When the molecular weight of the gelatin is made low by amethod of enzymatic decomposition or the like, the viscosity can belowered. The molecular weight of gelatin is preferably from 5,000 to100,000, more preferably 50,000 or less, and most preferably 30,000 orless. When gelatin is used for the crystal growth, the gelatin addedtogether with the silver halide grain has an influence on the thicknessof the tabular silver halide grains. The influence on the thickness canbe variously changed by the chemical modification of gelatin. In orderto obtain thin tabular silver halide grains, an oxidizing treatment, asuccinic acid treatment or a trimellitic acid treatment is preferablyused.

[0176] The mixing for the formation of the silver halide grains in theinvention is not the mixing by a turbulent flow that has conventionallybeen used, but the mixing utilizing a laminar flow. In the mixing inaccordance with the present invention, the silver nitrate solution andthe halide solution are subdivided into thin layers (lamellas), and theyare respectively brought into contact with each other at a large area,so that ions are diffused uniformly in a short time, and more rapid andmore uniform mixing are realized. The movement of an ion by diffusion isgiven by the following expression in terms of a diffusion coefficientand a temperature gradient in accordance with the Fick law that relatesthe change of temperature to time;

t˜dl²/D

[0177] wherein, D denotes a diffusion constant, dl denotes a thicknessof a thin layer, and t denotes a mixing time.

[0178] From the above expression, since the mixing time t is inproportion to the square the thickness dl of the thin layer, the mixingtime can be shortened very effectively by thinning this layer.

[0179] That is, the principle is based on multi-lamination of a fluidand subsequent diffusion mixing. The fluids of the silver salt solutionand the halide solution pass through intricate slits having a thicknessof several tens microns, so that they are divided into a large number ofthin layers fluids, they come into contact with each other at the exitsof the slits in the normal direction of the traveling direction and in awide area, the diffusion of silver ions and halogen ions startsimmediately, the mixing due to the diffusion is completed in a shorttime, and micro grains of silver halide are formed by ionic reactionswhich take place simultaneously.

[0180] The reaction in the invention takes place while the fluids areflowing in a flow passage, that is, in a flowing state.

[0181] The thickness of the thin layer in the invention is from 1 μm to900 μm in the normal direction to the traveling direction, preferablyfrom 1 μm to 300 μm. The mixing time in the invention utilizing thelaminar flow varies with the diffusion time of a mixture or reactants,and is preferably from 0.5 second to 2 minutes, more preferably from 1second to 1 minute. In the case of less than 0.5 second, although themixing time varies with the diffusion distance and the diffusion rate,mixing and reaction accompanied by the mixing may be insufficient.Further, in the case of exceeding 2 minutes, the mixing becomes similarto that of a batch type-agitating container, and an effect of using amicroreactor lessens.

[0182] The microreactor used in the invention is a device including aflow passage (microchannel) having an equivalent diameter of 500 μm orless per one introduction flow passage. The equivalent diameter in theinvention is called also a nominal diameter, and is a term used in themechanical engineering. When a circular pipe equivalent to a pipe (flowpassage in the invention) having an arbitrary cross-sectional shape isconsidered, the diameter of the equivalent circular pipe is called theequivalent diameter. When A is a cross-sectional area of the pipe, and Pis wetted perimeter length (peripheral length) of the pipe are used, theequivalent diameter is defined as deq=4A/p. In the case where it isapplied to a circular pipe, the equivalent diameter is coincident withthe diameter of the circular pipe. The equivalent diameter is used forestimating the fluidity or the thermal conduction properties in the pipeon the basis of data of the equivalent circular pipe, and represents thespatial scale (typical length) of a phenomenon. The equivalent diameterbecomes deq=4a²/4a=a for a square pipe having one side a, deq=a/3^(1/2)for an equilateral triangle pipe having one side a, and deq=2h for aflow between parallel flat plates with a height (see “MechanicalEngineering Dictionary” edited by Japanese Mechanical Society, 1997,Maruzen Co.).

[0183] Although the length of a flow passage used in the invention isnot particularly restricted, it is preferably from 1 mm to 1000 mm, morepreferably from 10 mm to 500 mm.

[0184] It is not necessary that the number of flow passages used in theinvention is one, and plural flow passages can be provided in parallel(numbering-up) as the need arises, so that the throughput can beincreased.

[0185] The flow passage of the invention is prepared on a solidsubstrate by micro-fabricating technologies. An example of a material tobe used includes metal, silicon, TEFLON™, glass, ceramic and plastic.When heat resistance, pressure resistance, and solvent resistance arenecessary, a preferable material includes silicon, TEFLON™, glass andceramic, and especially preferably metal. An example of metal includesnickel, aluminum, silver, gold, platinum, tantalum, stainless, hastelloy(Ni—Fe alloy), and titanium, and preferably stainless having highcorrosion resistance, hastelloy and titanium. In the conventional batchtype reaction apparatus, when an acidic material or the like is handled,an apparatus in which the metal (stainless etc.) surface is lined withglass is used. Similarly, the metal surface may be lined with glass inthe microreactor. In addition to glass, according to an object, metalmay be coated with another metal or another material, and a material(for example, ceramic) other than metal may be coated with metal orglass.

[0186] A typical micro-fabricating technology for preparing a flowpassage includes an LIGA technology using an X-ray lithography, a highaspect ratio photolithography method using EPON SU-8, a micro-electricdischarge machining process (μ-EDM), a high aspect ratio machiningmethod of silicon by Deep RIE, a Hot Emboss machining method, a lightshaping method, a laser machining method, an ion-beam machining method,and a mechanical micro-cutting work method using a micro-tool made ofhard material such as diamond. These technologies may be singly used, ormay be used in combination. A preferable micro-fabricating technologyincludes the LIGA technology using X-ray lithography, the high aspectratio photolithography using EPON SU-8, the micro-electric dischargemachining method (P-EDM), and the mechanical micro-cutting work method.

[0187] When the microreactor of the invention is assembled, a joiningtechnique is often used. A normal joining technique is roughly dividedinto solid-phase joining and liquid-phase joining. In joining methodsgenerally used, a typical joining method includes, pressure welding anddiffusion bonding as the solid-phase joining, and welding, eutecticbonding, brazing, and gluing as the liquid joining. Further, at the timeof assembling, it is desirable to use a highly precise joining method inwhich dimension accuracy is maintained in such a way that deteriorationof material due to high temperature heating, or destruction of amicro-structure such as a flow passage by a large deformation ofmaterial does not take place. Such technique includes a silicon directjoining, anode joining, surface activation joining, direct joining usinghydrogen bonding, joining using aqueous HF solution, Au—Si eutecticbonding, and void-free bonding.

[0188] The flow passage of the microreactor of the invention may besubjected to a surface treatment according to an object. In particular,when a surface is treated with an aqueous solution, since the adsorptionof a sample to glass or silicon may become a problem, the surfacetreatment is important. In the fluid control in the micro-sized flowpassage, it is desirable to realize this without incorporating a movablepart requiring a complicated manufacturing process. For example, ahydrophilic region and a hydrophobic region are prepared in the flowpassage by the surface treatment, so that it becomes possible to treat afluid by using a difference in surface tension exerting on the boundarybetween these regions.

[0189] In order to introduce a reagent or a sample into the micro-sizedflow passage of the microreactor to effect mixing, a fluid controlfunction is necessary. Especially, since the behavior of a fluid in amicro region has a property different from that in a macro scale, acontrol system suitable for the micro scale must be taken intoconsideration. When fluid control systems are classified in terms of theform, the fluid control system includes a continuous flow system and adroplet (liquid plug) system. When classified in terms of the drivingforce, the system includes an electrical driving system and a pressuredriving system. These systems will be described below in detail. As theform for handling a fluid, the continuous flow system is most widelyused. In the fluid control of the continuous flow type, the inside ofthe whole flow passage of the microreactor is filled with the fluid, andthe whole fluid is generally driven by a pressure source such as asyringe pump provide at the exterior of the passage. In this case,although one advantage is that the control system can be realized by arelatively simple setup, there are disadvantages that reactioncomprising a plurality of steps or manipulation accompanied by anexchange of samples is difficult, the degree of freedom concerning thesystem constitution is low, and a dead volume is large since an actionmedium is a solution itself. As a system different from the continuousflow system, there is a droplet (liquid plug) system. In this system,droplets partitioned by air are moved in the inside of a reactor or aflow passage leading to the reactor, and each droplet is driven by airpressure. At this time, it is necessary that a vent structure forreleasing the air between the droplet and the wall of the flow passage,or between the droplets to the outside as the need arises, and a valvestructure for keeping the pressure in a branched flow passageindependently from other portions are provided in the inside of thereactor system. In addition, in order to perform the manipulation of thedroplet by controlling the pressure difference, it is necessary toconstruct a pressure control system comprising a pressure band and aselector valve at the outside of the reactor. In the liquid dropletsystem, although the apparatus configuration and the structure of thereactor become rather complicated as stated above, a multi-stageoperation is enabled, for example, plural droplets are individuallyoperated and some reactions are sequentially performed, and the degreeof freedom concerning the system configuration becomes high.

[0190] As the driving system for performing the fluid control, there aregenerally and widely used an electrical driving method in which a highvoltage is applied between both ends of a flow passage (channel) togenerate an electro-osmotic flow, thereby fluid is moved, and a pressuredriving method in which a pressure band is provided at the outside ofthe passage and a pressure is applied to a fluid to move the fluid. Ithas been known that both systems are different in that, for example, asthe behavior of the fluid, the flow rate profile in the cross-section ofthe flow passage becomes a flat distribution in the case of theelectrical driving system, whereas it becomes a hyperbolic flowdistribution in the pressure driving system, in which the flow rate ishigh at the center of the flow passage and low at the wall surface part.Therefore, the electrical driving system is suitable for such an objectthat a movement is made while the shape of a sample plug or the like iskept. In the case where the electrical driving system is performed,since it is necessary that the inside of the flow passage is filled withthe fluid, the form of the continuous flow system must be adopted.However, since the fluid can be treated by an electrical control, acomparatively complicated process is also realized, for example, aconcentration gradient varying with time is formed by continuouslychanging the mixing ratio of two kinds of solutions. In the case of thepressure driving system, the control can be made irrespective ofelectrical properties of the fluid, and secondary effects such as heatgeneration or electrolysis may not be considered, and therefore, aninfluence on the base quality hardly exists, and its application rangeis wide. On the contrary, a pressure source must be prepared outside,and for example, response characteristics to manipulation are changedaccording to the magnitude of a dead volume of a pressure system, and itis necessary to automate the complicated process.

[0191] Although a method used as a fluid control method is suitablyselected according to its object, the pressure driving system of thecontinuous flow system is preferable.

[0192] The temperature control of the microreactor may be performed byputting the whole device in a container in which the temperature iscontrolled, or a heater structure such as a metal resistance wire orpolysilicon is formed in the device and a thermal cycle may be performedin such a manner that the heater structure is used when heating, andcooling is natural cooling. With respect to the sensing of temperature,when a metal resistance wire is used, the same resistance wire as theheater is additionally formed, and the temperature detection isperformed on the basis of the change of the resistance value of theadditional wire. When the polysilicon is used, a thermocouple is used todetect the temperature. Further, heating and cooling may be performedfrom the outside by bringing a Peltier element into contact with thereactor. A suitable method is selected in accordance with the use, thematerial of the reactor body and the like.

[0193] The details of the microreactor are described in Section 3 of“Microreactor” (W. Ehrfeld, V. Hessel, H. Loewe, 1 Ed. (2000)WILEY-VCH), and the micro heat exchanger is described in Section 4thereof.

[0194] Next, a second embodiment of the invention will be described withreference with FIGS. 3 to 5.

[0195]FIG. 3 is a whole schematic structural view showing a productionsystem according to a first structural example of the second embodiment.The production system according to the first structural example shown inFIG. 3 is intended to scale up the production scale by using a pluralityof microreactors for each step or process in a pre-ripening process (anucleus forming process, a first crystal growing process, and a secondcrystal growing process), and an after-ripening process. The number ofparallel devices is from 1 to 10,000, preferably from 1 to 100.

[0196] In the production apparatus of the silver halide photographicemulsion according to this first structural example, the liquidchemicals for producing the emulsion which are obtained through nucleusforming processes by a plurality of microreactors (A1 to An) 30 and inwhich microcrystals of silver halide are dispersed in protective colloidsolutions, are collected by liquid guiding pipes 56, and are againdistributed through the liquid guiding pipes 56 to a plurality of heatexchange microreactors A32 (the number of the parallel devices is from 1to 10,000, preferably from 1 to 100), and the temperature control andphysical ripening process are carried out.

[0197] Next, in the production apparatus of the first structuralexample, the liquid chemicals for producing the emulsion which aresubjected to the temperature control by the plural heat exchangemicroreactors A32 and are adjusted to predetermined temperature, arecollected by the liquid guiding pipes 56, and are again distributedthrough the liquid guiding pipes 56 to a plurality of microreactors (B1to Bn) 34, and the first crystal growing process is carried out.

[0198] Next, in the production apparatus of the first structuralexample, the liquid chemicals for producing the emulsion which aresubjected to the first crystal growing process by the pluralmicroreactors (B1 to Bn) 34 and in which nuclei 44 of middle crystals ofsilver halide are dispersed in the aqueous protective colloid solutions,are collected by the liquid guiding pipe 56, and are again distributedthrough the liquid guiding pipe 56 to plural microreactors (C1 to Cn)36, and liquid chemicals for producing an emulsion produced by pluralmicroreactors (D1 to Dn) 38 are mixed, so that the second crystalgrowing process is carried out.

[0199] Next, in the production apparatus of the first structuralexample, the liquid chemicals for producing the emulsion which aresubjected to the second crystal growing process by the pluralmicroreactors (C1 to Cn) 36 and in which nuclei 46 of large crystals ofsilver halide are dispersed in the aqueous protective colloid solutions,are collected by the liquid guiding pipes 56 and are introduced to adesalting device 48. After a desalting process is carried out, theliquid chemicals are again distributed to a plurality of additionmicroreactors (A1 to An) 50 through the liquid guiding pipes 56, and theafter-ripening process is carried out.

[0200] In the production apparatus of the liquid chemicals for producingthe emulsion of the first structural example constituted as statedabove, the collection and distribution of the liquid chemicals forproducing the emulsion are repeated at each step of the pre-ripeningprocess (the nucleus forming process, the first crystal growing process,and the second crystal growing process) and the after-ripening process,so that the liquid chemicals for producing the emulsion are mutuallymixed and are uniform at the end points of the respective processes, andthe quality and characteristics of the silver halide photographicemulsion finally produced can be made uniform.

[0201] In the production apparatus of the liquid chemicals for producingthe emulsion constituted to have the series of lines, by suitablysetting the number of the microreactors (A1 to An) 30, the heat exchangemicroreactors A32, the microreactors (B1 to Bn) 34, the microreactors(C1 to Cn) 36, the microreactors (D1 to Dn) 38 or the microreactors (A1to An) 50 disposed at the respective processes according to theprocessing capacity and the like, the flow rates of the liquid chemicalsfor producing the emulsion between the respective processes becomeconstant, and the production apparatus can be constituted such that theprocess can be efficiently performed without stagnancy in the wholeproduction system.

[0202] Next, a second structural example of the second embodiment willbe described with reference to a whole schematic structural view of FIG.4 showing a production system. In the production system according to thesecond structural example shown in FIG. 4, in the foregoing structure ofthe first structural example in which each of the pre-ripening process(the nucleus forming process, the first crystal growing process, and thesecond crystal growing process), and the after-ripening process isperformed by using the plural microreactors to scale up the productionscale, a segmental process or treatment can be separated and performed.

[0203] In the production apparatus of the liquid chemicals for producingthe emulsion according to the second structural example, the liquidchemicals for producing the emulsion which are subjected to thetemperature control by plural heat exchange microreactors A32 and areadjusted to predetermined temperature, are collected through liquidguiding pipes 56 and are stored in a storage tank 58.

[0204] In the storage tank 58, temperature adjustment and agitation ofthe liquid chemicals for producing the emulsion are performed by using atemperature control means and agitating means of the liquid chemicalsfor producing the emulsion, if necessary, to mix the liquid chemicalsfor producing the emulsion to be uniform, so that the liquid chemicalscan be stored under suitable conditions.

[0205] Next, in the production apparatus of the second structuralexample, the liquid chemicals for producing the emulsion stored in thestorage tank 58 are distributed to a plurality of microreactors (B1 toBn) 34 through the liquid guiding pipes 56 at a predetermined timing,and the first crystal growing process is carried out.

[0206] Incidentally, the storage tank 58 may be installed at a single orplural places between the respective processes as occasion demands.

[0207] In the production apparatus of the liquid chemicals for producingthe emulsion according to the second structural example constituted asstated above, as exemplified in FIG. 4, the storage tank 58 is installedbetween the nucleus forming process and the first crystal growingprocess in the pre-ripening process, so that the operation can be madeto proceed in such a way that only the nucleus forming process is firstperformed, and at a subsequent suitable timing, each of the subsequentsecond crystal growing process, the after-ripening process, and thedesalting process is performed.

[0208] Further, the process liquids processed by the plurality ofmicroreactors C36 may be collected and the desalting process maybeperformed by one desalting device 48, or maybe performed by respectivedesalting devices 48 corresponding to each microreactor C36.

[0209] Incidentally, since the structure, operation and effect of thesecond structural example of the second embodiment other than the abovedescription are the same as the foregoing first embodiment or the firststructural example of the second embodiment, the detailed descriptionsare omitted.

[0210] Next, a third structural example of the second embodiment will bedescribed with reference to a whole schematic structural view of FIG. 5showing a production system. In the production system according to thethird structural example as shown in FIG. 5, in the structure forscaling up the production scale by using plural production apparatusesof silver halide photographic emulsion in parallel, each of which isconstituted to have a single line in series using the foregoingmicroreactor shown in FIG. 1, a part of process or treatment isseparated and can be performed.

[0211] In the production apparatus of the silver halide photographicemulsion according to the third structural example, the liquid chemicalsfor producing the emulsion which have been subjected to the nucleusforming process by a plurality of microreactors A30 provided in paralleland have been fed, and in which microcrystals of silver halide aredispersed in an aqueous protective colloid solution, are introduced intorespective heat exchange microreactors A32. The liquid chemicals forproducing the emulsion subjected to temperature control and adjusted topredetermined temperature by the respective reactors are collected byrespective liquid guiding pipes 56 and are stored in a storage tank 58.

[0212] In this storage tank 58, if necessary, the temperature adjustmentand agitation of the liquid chemicals for producing the emulsion areperformed by using a temperature control means of the liquid chemicalsfor producing the emulsion and an agitating means, and the liquidchemicals for producing the emulsion are mixed to be uniform, and can bestored under suitable conditions.

[0213] Next, in the production apparatus of the third structuralexample, the liquid chemicals for producing the emulsion stored in thestorage tank 58 are distributed to a plurality of microreactors (B1 toBn) 34 through the respective liquid guiding pipes 56 at predeterminedtiming and the first crystal growing process is carried out.

[0214] Incidentally, the storage tank 58 may be installed at a singleplace or plural places between the respective processes as occasiondemands.

[0215] In the production apparatus of the silver halide photographicemulsion according to the third structural example structured as statedabove, as exemplified in FIG. 5, the storage tank 58 is installedbetween the nucleus forming process and the first crystal growingprocess in the pre-ripening process, so that the operation can be madeto proceed in such a way that only the nucleus forming process is firstperformed, and at a subsequent suitable point of time, each of thesubsequent second crystal growing process and the after-ripening processis performed.

[0216] In the production apparatus of the silver halide photographicemulsion according to the third structural example, the pluralmicroreactors A30 provided in parallel and the heat exchangemicroreactors A32 to make counterparts thereto are respectively dividedinto a plurality of groups, nuclei having different in characteristicsare formed in the respective groups, the liquid chemicals for producingthe emulsion containing the nuclei having different characteristics arecollected through the respective liquid guiding pipes 56, are collectedin the storage tank 58, and are blended to be uniform for use.

[0217] Further, the uniform liquid chemicals for producing an emulsioncontaining the nuclei having the same characteristics which have beencollected in the storage tank 58 are supplied to those obtained bydividing plural microreactors B34, microreactors C36, microreactors D38,desalting devices 48 and microreactors for addition A50, which areprovided in parallel, into a plurality of groups, respectively. Thesecond crystal growing process, after-ripening process, and liquidpreparation process that are different from each other for each groupare carried out, so that the silver halide photographic emulsions havingdifferent characteristics can be produced.

[0218] In addition, in a configuration (not shown) in which a pluralityof the production apparatuses of silver halide photographic emulsionconstituted to have a single line in series using the foregoingmicroreactor shown in FIG. 1, are used in parallel to scale up theproduction scale, the plurality of single lines in series are puttogether to make one-system production apparatus, the plural lines ofthe one system are divided into two or more groups, and the silverhalide photographic emulsions having different characteristics or otherchemicals may be produced for each group. In this case, the number ofparallel lines in one system is from 1 to 10000, preferably from 1 to100. Further, the number of parallel systems in multiple systems is from1 to 10000, preferably from 1 to 100.

[0219] In this way, a plurality of production apparatuses of silverhalide photographic emulsion, each of which is constituted to have asingle line in series, are put together to form one-system productionapparatus, the one-system production apparatus is divided into two ormore groups, and two or more kinds of emulsions are simultaneouslyproduced in the respective groups, so that multiple kinds of emulsionscan efficiently be carried out.

[0220] By constructing the production system in this way, each of theproduction apparatuses of the silver halide photographic emulsion havinga number of single lines in series can be effectively used.

[0221] Further, only a desired portion in the production apparatuses ofthe silver halide photographic emulsion having a number of series ofsingle lines for constituting the production system is used forperforming the process corresponding to the portion, so that theproduction system is effectively used in part.

[0222] Since the structure, operation and effect of the third structuralexample of the second embodiment other than the above description arethe same as the first embodiment or the first structural example of thesecond embodiment, the detailed descriptions are omitted.

[0223] In a configuration (not shown) in which a plurality of theproduction apparatuses of silver halide photographic emulsionconstituted to have a single line in series using the foregoingmicroreactor shown in FIG. 1, are used in parallel to scale up theproduction scale, the total production quantity can be controlled by thenumber of the production apparatuses of silver halide photographicemulsion, each of which is constituted to have a single line in seriesand is simultaneously used in parallel, and their operation time. Inaddition a high quality and high performance of the silver halidephotographic emulsion thus produced can be kept constant.

[0224] Thus, in the case where a desired quantity of silver halidephotographic emulsion is produced, for example, when it is desired toproduce only a desired quantity of silver halide photographic emulsionin a short time, the production apparatuses of the silver halidephotographic emulsion having a relatively large number of lines inseries corresponding to the desired quantity is used for production, andwhen a desired quantity of silver halide photographic emulsion isproduced over a long period of time, the production apparatuses of thesilver halide photographic emulsion having a relatively small number oflines in series is used for production, so that the high quality, highperformance and uniform silver halide photographic emulsion can beproduced.

[0225] Further, in the case where a predetermined quantity of silverhalide photographic emulsion is produced in a predetermined time, thetotal number of production apparatuses of silver halide photographicemulsion to be used, each of which is constituted to have a single linein series, is calculated from the production quantity per unit in theproduction apparatus of the silver halide photographic emulsion havingthe single line in series and a predetermined production time, and aso-called tailor-made production apparatus satisfying these conditionscan be temporarily or permanently constituted.

[0226] That is, by adjusting the number (so-called line number) ofproduction apparatuses of silver halide photographic emulsion, to beused simultaneously in parallel, and the production time, each of theapparatuses being constituted to have a single line in series, it ispossible to constitute a collective unit of the production apparatusesof silver halide photographic emulsion, which meets an arbitraryproduction quantity in total, and can produce the high quality, highperformance and uniform silver halide photographic emulsion.

[0227] In this way, for example, in the case where the silver halidephotographic emulsion is produced by the batch system using a tankhaving a large capacity as in a conventional manner, only a fixed largequantity of silver halide photographic emulsion can be produced, so thatan excess amount of silver halide photographic emulsion must bediscarded and wasted, but in the production apparatus of the silverhalide photographic emulsion constituted to have the single line inseries according to this embodiment, the waste can be eliminated.

[0228] Further, in a conventional method, when the silver halidephotographic emulsion is manufactured by a batch system using a tankhaving a large capacity, the time required for completing one productionoperation is constant. However, according to the present embodiment, theproduction apparatus of the silver halide photographic emulsionconstituted to have a single line in series has adaptability, forexample, the production time can be shortened or lengthened, so that thecooperation with other production lines is realized, and theproductivity can be improved as a whole.

[0229] In addition, in a conventional method, when the silver halidephotographic emulsion is manufactured by a batch system using a tankhaving a large capacity, the performance and quality of the silverhalide photographic emulsions produced by the tank having a largecapacity deviate slightly from each other. In contrast, in theproduction apparatus of the silver halide photographic emulsionconstituted to have the single line in series according to the presentembodiment, the performance and quality of all of the produced silverhalide photographic emulsions can be made uniform.

[0230] Next, a third embodiment of the present invention will bedescribed with reference to FIGS. 6 to 8.

[0231] The gist of the third embodiment is as follows.

[0232] First, a production apparatus of silver halide photographicemulsion is constituted by a nuclei forming and two-liquid mixingmicroreactor for producing a sliver halide grain by introducing a silversalt solution and a halide solution to cause a silver ion and a halogenion to react with each other, and a nuclei stabilizing and two-liquidmixing microreactor for introducing a reaction solution which has beensubjected to a silver halide nucleus forming reaction by being connectedto the nucleus forming and two-liquid mixing microreactor, andintroducing water or an aqueous protective colloid solution toinstantaneously mix the reaction solution and the water or the aqueousprotective colloid solution, so that a distance between nucleus grainsis extended to stabilize the nucleus grains.

[0233] By the constitution as described above, immediately after thenuclei of silver halide are formed by the nucleus forming reactionmicroreactor, the reaction solution is introduced into the nucleus grainstabilizing microreactor, the reaction solution and the water or theaqueous protective colloid solution are instantaneously mixed to extendthe distance between the nucleus grains and the process of stabilizingthe nucleus grains is performed, so that the grains are separated as faras possible so as not to occur a nucleus forming reaction and a graingrowth reaction simultaneously, and after the nucleus grains of thesilver halide emulsion formed by the nucleus forming reaction are stablytaken out, the grain growth reaction is suitably promoted, so that monodispersed silver halide emulsion grains can be finally produced.

[0234] Further, the silver halide photographic emulsions having uniformemulsion performance can be produced by the microreactor. In addition,since the microreactor is used, a small production system can be easilyscaled up to a mass production system, and the emulsion production isenabled at an optimum production scale corresponding to a requiredproduction quantity.

[0235] Second, a production apparatus of silver halide photographicemulsion is constituted by a nucleus forming reaction and three-liquidmixing microreactor for producing nucleus grains of silver halide byintroducing water or an aqueous protective colloid solution from a firstflow passage to form a straightened lamella-shaped laminar flow,introducing a silver salt solution from a second flow passages to form astraightened lamella-shaped laminar flow, bringing the silver saltsolution into contact with one contact interface of the laminar flow ofthe water or the aqueous protective colloid solution, and introducing ahalide solution from a third flow passage to form a straightenedlamella-shaped laminar flow, and bringing the halide solution, as thestraightened flow of the thin layer, into contact with the other contactinterface of the laminar flow of the water or the aqueous protectivecolloid solution so as not come into direct contact with the laminarflow of the silver salt solution, so that a silver ion and a halogen ionare diffused and moved in the water or the aqueous protective colloidsolution to allow to react with each other; and a nucleus grainstabilizing and two-liquid mixing microreactor for introducing areaction solution which contains the water or the aqueous protectivecolloid solution and is subjected to a silver halide nucleus formingreaction by being connected to the nucleus forming reaction andthree-liquid mixing microreactor, and newly introducing water or anaqueous protective colloid solution to instantaneously mix the reactionsolution and the new water or the aqueous protective colloid solution,so that a distance between nucleus grains is extended to stabilize thenucleus grains.

[0236] By the constitution as described above, in the inside of thenucleus forming reaction and three-liquid mixing microreactor, whenviewed microscopically, a single silver ion and a single halogen iondispersed at suitable intervals in the water or the aqueous protectivecolloid solution meet each other in one-to-one correspondence, and arebonded to form a nucleus. The control is performed such that heatgenerated at this time is absorbed by the water or the aqueousprotective colloid solution around the nuclei of silver halide tosuppress the Ostwald ripening, so that the nuclei are separated so asnot to occur a nucleus forming reaction and a grain growth reactionsimultaneously, the nuclei of silver halide formed by the nucleusforming reaction are stably taken out, the reaction solution containingthe nuclei of silver halide is introduced into the nucleus grainstabilizing and two-liquid mixing microreactor, and the reactionsolution and the water or the aqueous protective colloid solution areinstantaneously mixed to further extend the distance between the nucleusgrains and to perform the process of stabilizing the nucleus grains, sothat the grains are sufficiently separated so as not to occur thenucleus forming reaction and the grain growth reaction simultaneously,and after the nucleus grain of silver halide emulsion formed by thenucleus forming reaction is stably taken out, the grain growth reactionis suitably accelerated, so that the mono dispersed silver halideemulsion particles can be finally produced. That is, the sizedistribution of the nucleus grains is made narrow so that the crystalsof the nucleus grains become only those having a desired single crystalstructure, and it becomes possible to unify the shape, size and numberof the nucleus grains, the growth reaction becomes easy to perform, andthe crystal shape of the final grain and the size distribution can bemade more uniform.

[0237] It is also possible to produce the silver halide photographicemulsion having uniform emulsion performance by the microreactor.Further, since the microreactor is used, a small production system canbe easily scaled up to a mass production system, and, the emulsion canbe produced at an optimum production scale corresponding to a requiredproduction quantity.

[0238] Third, in the production apparatus of the silver halidephotographic emulsion as described above in the first or the second,temperature control means for performing a temperature control of anobjective reaction solution is provided in the nucleus forming andtwo-liquid or three-liquid mixing microreactor and/or the nucleus grainstabilizing and two-liquid mixing microreactor.

[0239] By the constitution as described above, the nucleus forming andtwo-liquid or three-liquid mixing microreactor and/or the nucleus grainstabilizing and two-liquid mixing microreactor makes a heat exchangewith the objective reaction solution introduced into the inside of themicroreactor by the temperature control means to perform a rapidtemperature control of the objective reaction solution. By this, thenucleus forming and two-liquid or three-liquid mixing microreactorand/or the nucleus stabilizing and two-liquid mixing microreactor, whichare provided with the temperature control means, suitably executes thetemperature control at the time when the silver halide nucleus formingreaction is made to occur, and the silver halide nucleus formingreaction can be more precisely controlled.

[0240] Namely, in the nucleus forming and two-liquid or three-liquidmixing microreactor and/or the nucleus grain stabilizing and two-liquidmixing microreactor, which are provided with the temperature controlmeans, since heat energy is transmitted in an infinitesimal state inwhich the reaction solutions form thin layers, the temperature changerapidly takes place to the objective set temperature, so that it can besaid that a deviation of timing of temperature change does not occurbetween the infinitesimal reaction solutions forming the thin layers inthe inside of the microreactor. Thus, it is possible to preventdifference in the formed chemical materials due to the difference in thehistory of temperature change.

[0241] Further, in the case where the temperature control is performedby the nucleus forming and two-liquid or three-liquid mixingmicroreactor and/or the nucleus stabilizing and two-liquid mixingmicroreactor, which are provided with the temperature control means, theheat energy is exchanged with the infinitesimal reaction solutions whichform the thin layers and flow in the inside of the microreactor, and thetemperature change of the reaction solutions is completed in a shorttime. Thus, in the case where the temperature control is performed bythe nucleus forming and two-liquid or three-liquid mixing microreactorand/or the nucleus stabilizing and two-liquid mixing microreactor, whichare provided with the temperature control means, a waiting time from thestart of the temperature change of the reaction solutions to thecompletion is eliminated, and the total processing time can be greatlyreduced. In addition, in the case where temperature control is performedby the nucleus forming and two-liquid or three-liquid mixingmicroreactor and/or the nucleus stabilizing and two-liquid mixingmicroreactor, which are provided with the temperature control means, therate of the temperature change of the liquid chemicals for producing theemulsion is high (high responsiveness to the temperature change), andthere is no stagnation and no recycling flow, so that the controloperation of temperature of the liquid chemicals for producing theemulsion can be precisely controlled, and an appropriate silver halidephotographic emulsion can be produced by a subsequent process.

[0242] (Third Embodiment)

[0243]FIG. 6 is a schematic view of a nucleus forming reactionmicroreactor 60 for performing a nucleus forming process in the grainformation of a silver halide emulsion in a pre-ripening process in aproduction apparatus of silver halide photographic emulsion of theinvention and a nucleus growth reaction controlling microreactor 62(corresponding to the process of the microreactor A30 of FIG. 1).

[0244] The pair of the nucleus forming reaction microreactor 60 and thenucleus growth reaction controlling microreactor 62 are designed suchthat a nucleus forming reaction and a grain growth reaction during thetime of grain formation of silver halide photographic emulsion isseparated as far as possible so that the nucleus forming reaction andthe grain growth reaction do not simultaneously occur at the time of theformation of the silver halide grains, and after the nucleus grains ofthe silver halide emulsion formed by the nucleus forming reaction isstably taken out, the grain growth reaction is suitably accelerated,whereby the mono dispersed silver halide emulsion grain can be finallyproduced.

[0245] The nucleus forming reaction microreactor 60 can be constitutedby using a general two-liquid mixing microreactor.

[0246] Here, the nucleus forming reaction microreactor 60 is formed suchthat a first flow passage into which a silver salt solution (fluid 1)flows and a second flow passage into which a halide solution (fluid 2)flows are formed, and parts of these two flow passages come in contactwith each other.

[0247] Further, the nucleus forming reaction microreactor 60 isconstituted as a device for continuously forming silver halide grains,in which each of these two fluids 1 and 2 (silver salt solution andhalide solution) substantially forms a thin layer, an open interface isformed between the adjacent fluids 1 and 2 (silver salt solution andhalide solution), the thicknesses of the thin layers of these two fluids1 and 2 (silver salt solution and halide solution) become 1 to 900 μmper layer in the normal direction of the contact interface, a silver ionand a halogen ion diffuse and move to the interface formed by the silversalt solution and the halide solution, and the silver ion and thehalogen ion react with each other, so that the silver halide grain iscontinuously produced.

[0248] In the nucleus forming reaction microreactor 60, since thenucleus formation is performed while the laminar flow flows in onedirection, the so-called local recycling in which nuclei circularly flowdoes not occur. Thus, when the nucleus formation is performed, it ispossible to prevent the occurrence of such a state that the so-calledlocal recycling occurs in which the once formed nuclei circularly flowand the growth simultaneously takes place.

[0249] In the case where the nucleus forming process is performed byusing the nucleus forming reaction microreactor 60, when viewedmicroscopically, a single silver ion and a single halogen ion are bondedin one-to-one correspondence. When a control is performed to absorb heatgenerated at this time and to suppress Ostwald ripening, a reaction forsuitably forming desired nuclei can be stably performed.

[0250] In addition, similarly to the nucleus forming reactionmicroreactor 60, the nucleus growth controlling microreactor 62 isconstituted as a general two-liquid mixing microreactor, and a firstflow passage for leading a reaction solution (fluid 1) sent from thenucleus forming reaction microreactor 60 and a second flow passage forleading water or an aqueous protective colloid solution (fluid 2) areformed, so that parts of these two flow passages come in contact witheach other.

[0251] Further, the nucleus growth controlling microreactor 62 isconnected to a process liquid discharge port of the nucleus formingreaction microreactor 60 and is disposed so that at the point of timewhen 60% or more, preferably 90% or more of the silver halide nucleusforming reaction occurring by diffusion in the nucleus forming reactionmicroreactor 60 is ended, this reaction solution is introduced to thenucleus growth reaction controlling microreactor 62.

[0252] The nucleus growth reaction controlling microreactor 62 uses thefunction of instantaneously mixing the reaction solution introduced fromthe first flow passage and the water or the aqueous protective colloidsolution introduced from the second flow passage, and performs a processof extending a distance between nucleus grains by making the water orthe aqueous protective colloid solution intervene between the nucleusgrains formed by the nucleus forming reaction.

[0253] When the distance between nucleus grains immediately after thenucleus forming reaction is instantaneously spread by the nucleus growthcontrolling microreactor 62 as stated above, since the nucleus formingreaction and the grain growth reaction can be separated while thenucleus forming reaction and the grain growth reaction do not occursimultaneously, after the nucleus grain of the silver halide emulsionformed by the nucleus forming reaction is stably taken out, it can besuitably guided to a process of performing the grain growth reaction.

[0254] That is, the size distribution of nucleus grains is made narrowso that crystals of nucleus grains become only those having desiredsingle crystalline structures exemplified in FIGS. 13A, 13B, 13C, 13D or13E, and the shape, size and number of nucleus grains can be madeuniform, so that the growth reaction becomes easy to perform, and thecrystal shape of the final grain and the size distribution can be mademore uniform.

[0255] The nucleus forming reaction microreactor 60 and the nucleusgrowth reaction controlling microreactor 62 are provided withtemperature control means capable of controlling temperatures of anobjective fluid at a rate of 3° C. per minute, preferably 5° C. orhigher by making a heat exchange between the objective fluid introducedinto the inside of the reactor and a temperature controlling mediumseparately introduced thereto.

[0256] In the case where the nucleus forming reaction microreactor 60and the nucleus growth controlling microreactor 62 are constituted asstated above, the temperature control at the time of performing thesilver halide nucleus forming reaction is suitably performed, and thesilver halide nucleus forming reaction can be more precisely controlled.

[0257] That is, in the case where the liquid chemicals for producing theemulsion in which the nucleus of silver halide is dispersed in theaqueous protective colloid solution is introduced in the inside of thenucleus forming reaction microreactor 60 by using the nucleus formingreaction microreactor 60 and the nucleus growth controlling microreactor62 provided with the temperature control means, and the temperaturecontrol is executed by making the heat exchange with the temperaturecontrol medium, since the heat energy is transmitted in an infinitesimalstate in which the liquid chemicals for producing the emulsion forms thethin layer, the temperature change is quickly performed to an objectiveset temperature.

[0258] Thus, in the case where the temperature control is performed bythe temperature control means of the microreactor, since it can be saidthat a deviation of the timing of the temperature change does not occurbetween the infinitesimal liquid chemicals for producing an emulsionforming the thin layers, it is possible to prevent a difference causedby a difference in the history of the temperature change from occurringin the formed chemical materials.

[0259] Further, in the case where the temperature control is performedby the temperature control means of the microreactor, the heat energy isexchanged with the infinitesimal liquid chemicals for producing anemulsion forming the thin layer and flowing in the inside of themicroreactor, and the temperature change of the liquid chemicals forproducing the emulsion is completed.

[0260] Thus, in the case where the temperature control is executed bythe temperature control means of the microreactor, it is possible toeliminate a waiting time from the start of the temperature change of theliquid chemicals for producing the emulsion to the completion. Forexample, in the case where a large quantity of liquid chemicals forproducing an emulsion is stored in a large tank, and a method of heatingthrough the outer peripheral wall of this tank is used, it takes a longwaiting time (waiting time of order of hours) for the large quantity ofliquid chemicals for producing an emulsion in the large tank to bechanged to a predetermined temperature, whereas in the case where thetemperature control is performed by the microreactor having thetemperature control means, this long waiting time (loss time) is omittedand the process time can be greatly shortened.

[0261] In addition to this, in the case where the temperature control isexecuted by the temperature control means of the microreactor, the rateof the temperature change of the liquid chemicals for producing theemulsion is high (high responsiveness to the temperature change), andthere is no stagnation and no recycling flow, so that the controloperation of temperature to the liquid chemicals for producing theemulsion can be precisely controlled, and accordingly, it is suitablyused for the nucleus forming process of silver halide in whichtemperature is a dominant factor of chemical change.

[0262] Next, a structural example of the third embodiment shown in FIG.7 will be described. FIG. 7 is a schematic view of a nucleus formingreaction microreactor 64 for performing a nucleus forming process ingrain formation of a silver halide emulsion in a pre-ripening processconcerning a production apparatus of silver halide photographic emulsionof the invention and a nucleus growth reaction controlling microreactor66 (corresponding to the process of the microreactor A30 of FIG. 1).

[0263] The nucleus forming reaction microreactor 64 is constituted as athree-liquid mixing microreactor.

[0264] Here, the nucleus forming reaction microreactor 64 is formed suchthat a first flow passage for leading a silver salt solution (fluid 1),a second flow passage for leading a halide solution (fluid 2), and athird flow passage for leading water or an aqueous protective colloidsolution (fluid 3) as an intermediate layer for preventing the formertwo solutions from immediately coming in contact with each other areformed, and adjacent parts of these three flow passages come in contactwith each other.

[0265] Further, the nucleus forming reaction microreactor 64 isconstituted as such a device that these three fluids 1, 2 (the silversalt solution and the halide solution) substantially form thin layers,open interfaces are formed between adjacent ones of the fluids 1, 2 and3 (the silver salt solution, the halide solution, and the water or theaqueous protective colloid solution), the thicknesses of the thin layersof these three fluids 1, 2 and 3 (the silver salt solution, the halidesolution, and the water or the aqueous protective colloid solution)become 1 to 900 μm per layer in the normal direction of the contactinterface, a silver ion and a halogen ion diffuse and move to theintermediate layer of the water or the aqueous protective colloidsolution provided between the silver salt solution and the halidesolution, and the silver ion and the halogen ion react with each otherso that a silver halide grain is continuously produced.

[0266] In the nucleus forming reaction microreactor 64, since thenucleus formation is performed while the laminar flow flows in onedirection, the so-called local recycling in which nuclei circularly flowdoes not occur. Thus, when the nucleus formation is performed, it ispossible to prevent the occurrence of such a state that the so-calledlocal recycling occurs in which the once formed nuclei circularly flowand the growth simultaneously takes place.

[0267] In the case where the nucleus forming reaction microreactor 64 isused for performing the nucleus forming process, when viewedmicroscopically, a single silver ion and a single halogen ion are bondedto each other in one-to-one correspondence. By performing the control toabsorb heat generated at this time and to suppress Ostwald ripening, thereaction of suitably forming desired nuclei can be stably performed.

[0268] Further, the nucleus growth reaction controlling microreactor 66is connected to a process liquid discharge port of the nucleus formingreaction microreactor 64 and is disposed so that at the point of timewhen 60% or more, preferably 90% or more of the silver halide nucleusforming reaction occurring by diffusion in the nucleus forming reactionmicroreactor 64 is ended, this reaction solution is introduced to thenucleus growth reaction controlling microreactor 66.

[0269] The nucleus growth reaction controlling microreactor 66 performsa process of spreading a distance between nucleus grains by theoperation of instantaneously mixing the reaction solution introducedfrom the first flow passage and the water or the aqueous protectivecolloid solution newly introduced from the second flow passage and bymaking the water or the aqueous protective colloid solution intervenebetween the nucleus grains formed by the nucleus forming reaction.

[0270] When the distance between grains immediately after the nucleusforming reaction is instantaneously extended relatively largely by thenucleus growth reaction controlling microreactor 66 as stated above,since the nucleus forming reaction and the grain growth reaction can besufficiently separated while this nucleus forming reaction and the graingrowth reaction do not occur simultaneously, after the nucleus grains ofthe silver halide emulsion formed by the nucleus forming reaction isstably taken out, it can be suitably guided to the process of performingthe grain growth reaction.

[0271] The nucleus forming reaction microreactor 64 and the nucleusgrowth reaction controlling microreactor 66 are constituted such that aheat exchange is made between an objective fluid introduced into theinside of the reactors and a temperature controlling medium separatelyintroduced, so that a temperature control of the objective fluid can beperformed at a rate of 3° C. per minute, preferably 5° C. or more.

[0272] In the case where the nucleus forming reaction microreactor 64and the nucleus growth reaction controlling microreactor 66 areconstituted as stated above, the temperature control when the silverhalide nucleus forming reaction is performed is suitably performed, andthe silver halide nucleus forming reaction can be more preciselycontrolled.

[0273] Next, a structural example of the third embodiment shown in FIG.8 will be described. FIG. 8 is a schematic view of a pre-processingmicroreactor 68 for performing a nucleus forming process in grainformation of the silver halide emulsion in the pre-ripening processconcerning the production apparatus of silver halide photographicemulsion of the present invention and a nucleus forming reactionmicroreactor 70 (corresponding to the process of the microreactor A30 ofFIG. 1).

[0274] Similarly to the structure shown in FIGS. 6 and 7, mono dispersedsilver halide emulsion grains can finally be produced by the pair of thepre-processing microreactor 68 and the nucleus forming reactionmicroreactor 70 by separating the nucleus forming reaction and the graingrowth reaction at the time of grain formation of silver halide emulsionas far as possible so that the nucleus forming reaction and the graingrowth reaction do not simultaneously occur at the time of formation ofthe silver halide grains, and by suitably accelerating the grain growthreaction after the nucleus grains of the silver halide emulsion formedby the nucleus forming reaction is taken out.

[0275] The pre-processing microreactor 68 and the nucleus formingreaction microreactor 70 can be respectively constituted by usinggeneral two-liquid mixing microreactors.

[0276] Here, the pre-processing microreactor 68 is formed such that afirst passage for leading a halide solution (fluid 1) and a second flowpassage for leading water or an aqueous protective colloid solution(fluid 2) are formed, and parts of these two flow passages come incontact with each other.

[0277] Further, the pre-processing microreactor 68 is constituted assuch a device that these two fluids 1 and 2 (the halide solution and thewater or the aqueous protective colloid solution) substantially formthin layers, an open interface is formed between the adjacent fluids 1and 2 (the halide solution and the water or the aqueous protectivecolloid solution), the thicknesses of the thin layers of these twofluids 1 and 2 (the halide solution and the water or the aqueousprotective colloid solution) become 1 to 900 μm per layer in the normaldirection of the contact interface.

[0278] Thus, in a microreactor 68, the interface is formed between theaqueous halide solution and the aqueous colloid solution, and halogenions which are formed from the halide through ionic dissociation thereofdiffuse into the interface, and subsequently, the halogen ions meet anaqueous silver nitrate solution in a microreactor 70, so that a suddennucleus forming reaction does not take place. In other words, thehalogen ions formed from the aqueous halide solution diffuse into alayer formed by the water or the aqueous protective colloid solution inaccordance with the concentration gradient of the halogen ions. Byutilizing the phenomenon, silver ions which diffuse from the aqueoussilver nitrate solution added to a microreactor 70 into the layersupplied from the microreactor 68 react with the halogen ions suppliedfrom the microreactor 68 in the vicinity of an interface formedtherebetween in the microreactor 70, so that the supply of halogen ionsfor the nucleus forming reaction is controlled in a silver halide grainforming device.

[0279] The nucleus forming reaction microreactor 70 is constituted as ageneral two-liquid mixing microreactor, and is formed such that a firstpassage for leading a mixed liquid (fluid 1) sent from thepre-processing microreactor 68 and a second flow passage for leading asilver salt solution (fluid 2) are formed, and parts of these two flowpassages come in contact with each other.

[0280] Further, the nucleus forming reaction microreactor 70 isconstituted as such a device that these two fluids 1 and 2 (what isobtained by mixing the halide solution with the water or the aqueousprotective colloid solution, and the silver salt solution) substantiallyform thin layers, an open interface is formed between the adjacentfluids 1 and 2 (what is obtained by mixing the halide solution with thewater or the aqueous protective colloid solution, and the silver saltsolution), the thicknesses of the thin layers of these two fluids 1 and2 (what is obtained by mixing the halide solution with the water or theaqueous protective colloid solution, and the silver salt solution)become 1 to 900 μm per layer in the normal direction of the contactinterface, a silver ion and a halogen ion move by diffusion to aninterface formed by what is obtained by mixing the halide solution withthe water or the aqueous protective colloid solution, and the silversalt solution, and the silver ion and the halogen ion react with eachother, so that the silver halide grain is continuously produced in astate where the water or the aqueous protective colloid solution is madeto intervene between the nucleus grains formed by the nucleus formingreaction to extend the distance between nucleus grains.

[0281] In the nucleus forming reaction microreactor 70, since thenucleus formation is performed while the flow of the laminar flow occursin one direction, the so-called local recycling in which a nucleuscircularly flows does not occur. Thus, when the nucleus formation isperformed, it is possible to prevent the occurrence of such a state thatthe so-called local recycling occurs in which the once formed nucleicircularly flow and the growth simultaneously occurs.

[0282] The pre-processing microreactor 68 and the nucleus formingreaction microreactor 70 are constituted such that a heat exchange ismade between an objective fluid introduced into the inside of thereactors and a temperature controlling medium separately introducedtherein, so that the temperature control of the objective fluids can beperformed at a rate of 3° C. per minute, preferably 5° C. or more perminute.

[0283] In the case where the pre-processing microreactor 68 and thenucleus forming reaction microreactor 70 are constituted as statedabove, the temperature control when the silver halide nucleus formingreaction is performed is suitably performed, and the silver halidenucleus forming reaction can be more precisely controlled.

[0284] Incidentally, since the structure, operation and effect of thethird embodiment other than the above description are similar to thefirst embodiment, the detailed descriptions are omitted.

[0285] Next, a fourth embodiment of the invention will be described withreference to FIG. 9.

[0286] The gist of the fourth embodiment is as follows.

[0287] First, a production apparatus of silver halide photographicemulsion is constituted by providing a reaction tank for producing asilver halide photographic emulsion, a circulating system for taking outa solution in the reaction tank to the outside and returning thesolution to the reaction tank through a mixer, and a nucleus formingmicroreactor in which, silver halide grains, which are produced bycausing a silver ion and a halogen ion to react with each other byintroducing a silver salt solution and a halide solution, are suppliedto the mixer and are mixed with the solution.

[0288] By the constitution as described above, the water or the aqueousprotective colloid solution in which the nucleus of small crystal ofsilver halide formed by the nucleus forming microreactor is quicklymixed into the dispersion medium solution in the tank by the mixer. Inthis way, feeding can be performed such that the nuclei of silver halidehaving a desired shape and size formed by the nucleus forming reactionare uniformly dispersed into the reaction tank.

[0289] In this way, the size distribution of the nucleus grains can bemade narrow, the shape, size and number of the nucleus grains can bemade uniform, the growth reaction becomes easy to perform in thesubsequent process, and the crystal shape of the final grain and thesize distribution can be made more uniform. Thus, it is possible toobtain the silver halide photographic emulsion having a high aspectratio, containing of tabular grains with a narrow grain sizedistribution, and uniform emulsion performance.

[0290] Further, since the microreactor is used, a small productionsystem can be easily scaled up to a mass production system, and theemulsion can be produced at an optimum production scale corresponding toa required production quantity.

[0291] Second, the production apparatus of the silver halidephotographic emulsion as described above in the first is constitutedsuch that a potential of a system is measured by a pAg measurementdevice provided in the reaction tank or the circulating system, the flowvolume of the silver nitrate solution and/or the halide solution addedto the nucleus forming microreactor is controlled, so that the potentialof the reaction system is controlled and the growth of nuclei iscontrolled.

[0292] By the constitution as described above, the operation of thenucleus growing process can be suitably performed in the reaction tankby automatic control.

[0293] Third, the production apparatus of the silver halide photographicemulsion as described in the first above is constituted such that a pHvalue of the reaction system is measured by a pH measurement deviceprovided in the reaction tank or the circulating system, and an acid oralkali is added into the mixer or the reaction tank, so that thereaction in the mixer and/or the pH value of the solution in thereaction tank is controlled to a predetermined condition, and the growthof the nuclei is controlled.

[0294] By the constructing as described above, the operation of thenucleus growing process can be suitably performed in the reaction tankby the automatic control.

[0295] (Fourth Embodiment) FIG. 9 is a schematic view exemplifying astructure in which a nucleus forming processing microreactor 72 and amixer 74 are provided in a sidearm emulsion preparation for performing anucleus forming process in the grain formation of a silver halidephotographic emulsion in a pre-ripening process concerning a productionapparatus of silver halide photographic emulsion of the invention.

[0296] As shown in FIG. 9, in the sidearm emulsion preparation, a tank76 as a reaction container (may be a reaction tank for performing graingrowth) is used. This tank 76 is constituted as a batch type reactioncontainer device provided with an agitator capable of processing a fixedlarge quantity, for example, 1000 1 (1 t) of liquid at a time.

[0297] An agitation vane 80 rotatively driven by a rotating drivingforce of a motor 78 is mounted in this tank 76 to agitate the solutionfilled in the inside of the tank.

[0298] Temperature control means 82 for heating or cooling the reactionsolution is disposed on the outer peripheral surface of the tank 76 toperform the temperature control of the solution filled in the inside ofthe tank. This temperature control means 82 is constituted by using, forexample, means for heating or cooling by causing a heat exchange medium(water, water vapor, liquid organic material, flame gas, etc.) to flowto a temperature control part or means for performing a temperaturecontrol by installing an element for electrically heating or cooling atthe temperature control section.

[0299] This tank 76 is equipped with a sidearm pipe passage 86 of acirculating system in which the solution in the tank 76 is taken outfrom the bottom, is fed by a pump 84, and is discharged to a liquidsurface side of the tank 76 through the mixer 74 to be returned into thetank 76.

[0300] In this sidearm pipe passage 86, it is desired that an additionliquid can be completely mixed with the solution in the tank in theshortest possible time, and it is not desirable that it takes a longtime to mix the addition liquid with the solution in the tank 76, theaddition liquid circulates in the inside of the sidearm pipe passage 86or the mixer 74, or it is partially circulated in some portion.Therefore, the large capacity pump 84 is mounted to the sidearm pipepassage 86 and the solution in the tank 76 is made to flow at arelatively large flow volume.

[0301] The mixer 74 installed in the sidearm pipe passage 86 isconstituted by providing a part of the flow passage in the sidearm pipepassage 86 provided outside of the tank 76, which leads to the mixer 74from the tank 76 and again returns to the tank 76, and by a passage forsupplying water or an aqueous protective colloid solution in whichnuclei of small crystals of silver halide formed in the nucleus formingprocessing microreactor 72 are dispersed, to the part of this passage.

[0302] Further, this mixer 74 is constituted such that mechanicalagitating means or static agitating means is used (it may be constitutedas a mixing microreactor), and the liquid in which the nuclei of thesmall crystals of silver halide are dispersed can be uniformly andinstantaneously mixed with a large quantity of solution flowing throughthe sidearm pipe passage 86 without causing partial circulation.

[0303] The nucleus forming processing microreactor 72 for supplying theliquid in which the nuclei of the small crystals of silver halide aredispersed, as the addition liquid, to this mixer 74 is constitutedsimilarly to the foregoing nucleus forming reaction microreactor 64exemplified in FIG. 7.

[0304] This nucleus forming reaction microreactor 72 is constituted as athree-liquid mixing microreactor.

[0305] Here, the nucleus forming reaction microreactor 72 is formed suchthat a first flow passage for leading a silver salt solution (fluid 1),a second flow passage for leading a halide solution (fluid 2), and athird flow passage for leading water or an aqueous protective colloidsolution (fluid 3) as an intermediate layer for preventing the fluids 1and 2 from immediately coming in contact with each other are provided,and adjacent parts of these three flow passages come in contact witheach other.

[0306] Incidentally, in order to process a required quantity of liquidby the microreactor 72, a plurality of such microreactors 72 are used toobtain the required quantity.

[0307] Further, the nucleus forming reaction microreactor 72 isconstituted such that these three fluids 1, 2 (the silver salt solutionand the halide solution) substantially form thin layers, respectively,open interfaces are formed between adjacent ones of the fluids 1, 2 and3 (the silver salt solution, the halide solution, and the water or theaqueous protective colloid solution), and the thicknesses of the thinlayers of these three fluids 1, 2 and 3 (the silver salt solution, thehalide solution, and the water or the aqueous protective colloidsolution) are within the range of 1 to 900 μm in the normal direction ofthe contact interface, preferably from 1 μm to 300 μm. A silver ion anda halogen ion diffuse and move to the intermediate layer of the water orthe aqueous protective colloid solution provided between the silver saltsolution and the halide solution, and the silver ion and the halogen ionreact with each other so that the silver halide grain is continuouslyproduced.

[0308] In the nucleus forming processing microreactor 72, a mixing timeusing the laminar flow is from 0.5 second to 2 minutes, more preferablyfrom 1 second to 1 minute. In the case of less than 0.5 second, althoughdependent on the diffusion distance or diffusion rate, mixing or areaction accompanied by mixing can be insufficient, and in the case ofmore than 2 minutes, it is close to a batch type agitation container,and the effect of using the microreactor declines.

[0309] In the nucleus forming reaction microreactor 72, since thenucleus formation is performed while the flow of the laminar flow occursin one direction, the so-called local recycling in which a nucleuscircularly flows does not occur. Thus, when the nucleus formation isperformed, it is possible to prevent the occurrence of such a state thatthe so-called local recycling occurs in which the once formed nucleicircularly flow and the growth simultaneously occurs.

[0310] In the case where the nucleus growing process is performed bythis sidearm emulsion preparation, a predetermined quantity of anaqueous dispersion medium solution containing at least a dispersionmedium and water is injected into the tank 76 from an emulsionintroduction pipe. Further, the motor 78 is driven and the agitationvane 80 is driven to be rotated to cause agitation, the temperaturecontrol is performed by the temperature control means 82 to keep thereaction solution in the tank 76 within a predetermined temperaturerange (for example, 5° C. to 45° C.), a state is produced in which forexample, nuclei of minute tabular grains including a parallel twinningplane can be formed, and the pump 84 is driven to set a state where theaqueous dispersion medium solution is circulated in the sidearm pipe 86.

[0311] When the nucleus forming process is performed by the sidearmemulsion preparation, since the water or the aqueous protective colloidsolution in which the nuclei of the small crystals of silver halideproduced by the nucleus forming processing microreactor 72 are rapidlymixed with the aqueous dispersion medium solution in the tank 76 by themixer 74, the aqueous dispersion medium solution, together with thewater or the aqueous protective colloid solution, is made to intervenebetween the nucleus grains formed by the nucleus forming reaction tofurther spread the distance between the nucleus grains, so that thenucleus forming reaction and the grain growth reaction do notsimultaneously occur, and the nucleus grains of the silver halideemulsion formed by the nucleus forming reaction can be stably stored inthe tank 76.

[0312] In this way, the size distribution of the nucleus grains is madenarrow, and the shape, size and number of the nucleus grains can be madeuniform, the growth reaction in the subsequent process becomes easy toperform, and the crystal shape of the final grains and the sizedistribution can be made more uniform. For example, it is possible toobtain the silver halide photographic emulsion having a high aspectratio and containing tabular grains having a narrow grain sizedistribution.

[0313] Although not shown, in the fourth embodiment, instead of thenucleus forming processing microreactor 72 and the mixer 74 in thesidearm emulsion preparation of performing the nucleus forming process,a mixer provided outside of the tank 76 may be constituted by providinga flow passage 1 for supplying a halide solution, a flow passage 2 forsupplying a silver nitrate solution, and a flow passage 3 for supplyinga solution containing protective colloid in the tank 76 from a flowpassage extending from the tank 76 to the mixer and again returning tothe tank 76, and by using a nucleus forming processing microreactor.

[0314] In the fourth embodiment, in the case where a structure isadopted such that a process for growing nuclei is performed in the tank76, the potential of the system is measured by a pAg measurement deviceprovided in the tank 76 or the sidearm pipe passage 86, the flow rate ofthe silver nitrate solution and/or halide solution to be added to thenucleus forming processing microreactor 72 is controlled to control thepotential of the reaction system, and the growth of the nuclei can becontrolled.

[0315] Further, in the fourth embodiment, in the case where a structureis adopted such that a process of growing nuclei is performed in thetank 76, pH value of the reaction system is measured by a pH measurementdevice provided in the tank 76 or the sidearm pipe passage 86, an acidor alkali is added to the mixer 74 or the tank 76 so that the reactionin the mixer 74 and/or the pH value of the solution in the tank 76 iscontrolled to a predetermined condition, and the growth of the nucleican be controlled.

[0316] Since the structure, operation and effect of the fourthembodiment other than the above descriptions are the same as those ofthe third embodiment, the descriptions are omitted.

[0317] Next, a fifth embodiment of the invention will be described withreference to FIGS. 10 to 12.

[0318] The gist of the fifth embodiment is as follows.

[0319] First, a production apparatus of silver halide photographicemulsion is constituted by providing a nucleus forming and two-liquidmixing microreactor for forming silver halide grains by introducing asilver salt solution and a halide solution and causing a silver ion anda halogen ion to react with each other, and a temperature control meansconstituted such that a change control is enabled to a temperature atwhich a diffusion rate of the silver ion and the halogen ion becomes 1.1times or more, preferably 1.5 times or more as high as a diffusion rateat a temperature of a reaction solution supplied to a reaction portionin the nucleus forming and two-liquid mixing microreactor, heatconduction is enabled to change the temperature of the reaction solutionat a rate of 5° C. or more per minute, preferably 10° C. or more perminute, more preferably 20° C. or more, a heat exchange range to thereaction solution is set so that a length of a time obtained by dividinga volume calculated from a length and depth of a microchannel in thenucleus forming and two-liquid mixing microreactor by a flow ratebecomes a length of a heat exchangeable time 5 times or less, preferably2 times or less as long as a diffusion time at a temperature of a liquidsupplied to the microreactor, and the diffusion rate of the silver ionand the halogen ion can be increased.

[0320] By the constitution as described above, since the diffusioncoefficient relates to the temperature, the diffusion rate can beincreased by raising the temperature, and accordingly, the diffusionrate of the silver ion and the halogen ion is increased to a desiredrate by heating the process liquid to enable the precise and efficientproduction, and the silver halide photographic emulsion having uniformemulsion performance can be produced by the microreactor in which thesilver halide nucleus forming reaction is controlled. In addition, sincethe microreactor is used, a small production system can be easily scaledup to a mass production system, and the emulsion production is enabledat an optimum quantity of production scale corresponding to a requiredproduction quantity.

[0321] Second, a production apparatus of silver halide photographicemulsion is constituted by providing a nucleus forming reaction andthree-liquid mixing microreactor in which water or an aqueous protectivecolloid solution is introduced from a first flow passage to form alaminar flow of a straightening thin layer shape and is made to flow, asilver salt solution is introduced from a second flow passage to form alaminar flow of a straightening lamella shape and is made to flow whilethe silver salt solution is brought into contact with one contactinterface of the laminar flow of the water or the aqueous protectivecolloid solution, and a halide solution is introduced from a third flowpassage to form a laminar flow of a straightening thin layer shape andis made to flow as a straightened flow of a thin layer in a state wherethe halide solution comes in contact with the other contact interface ofthe laminar flow of the water or the aqueous protective colloid solutionand does not come in direct contact with the laminar flow of the silversalt solution, so that a silver ion and a halogen ion diffuse and moveto the water or the aqueous protective colloid solution and react witheach other to form the nucleus grains of silver halide, and temperaturecontrol means constituted such that a change control is enabled to atemperature at which a diffusion rate of the silver ion and the halogenion becomes 1.1 times or more, preferably 1.5 times or more as high as adiffusion rate at a temperature of a reaction solution supplied to areaction portion in the nucleus forming, and two-liquid mixingmicroreactor, heat conduction is enabled to change the temperature ofthe reaction solution at a rate of 5° C. or more per minute, preferably10° C. or more per minute, more preferably 20° C. or more, a heatexchange range to the reaction solution is set so that a length of atime obtained by dividing a volume calculated from a length and depth ofa microchannel in the nucleus forming and two-liquid mixing microreactorby a flow rate becomes a length of a heat exchangeable time 5 times orless, preferably 2 times or less as long as a diffusion time at thetemperature of the liquid supplied to the microreactor, and thediffusion rate of the silver ion and the halogen ion can be increased.

[0322] By the foregoing constitution as described above, in the insideof the nucleus forming reaction and three-liquid mixing microreactor,when viewed microscopically, a silver halide nucleus forming reaction iscontrolled so that the diffusion rate of the single silver ion and thesingle halogen ion dispersed at suitable intervals in the water or theaqueous protective colloid solution is increased to a required rate, sothat the silver ion and the halogen ion meet each other precisely andefficiently in one-to-one correspondence to be bonded and to form anucleus. Since the distance between the nuclei of silver halide formedat this time is widened by the water or the aqueous protective colloidsolution around the nuclei, Ostwald ripening can be suppressed, andaccordingly, the nucleus forming reaction and the grain growth reactionare separated so that they do not occur simultaneously, and after thenuclei of silver halide formed by the nucleus forming process are stablytaken out, the grain growth reaction is suitably accelerated, so thatthe mono dispersed silver halide emulsion grains is finally formed. Thatis, the size distribution of the nucleus grains is made narrow so thatthe crystals of the nucleus grains become only those having a desiredsingle crystal structure, the shape, size and number of the nucleusgrains can be made uniform, the growth reaction becomes easy to perform,and the crystal shape and size distribution of the final grains can bemade more uniform. As stated above, the silver halide photographicemulsion having uniform emulsion performance can be produced by themicroreactor. Moreover, since the microreactor is used, a smallproduction system can be easily scaled up to a mass production system,and the emulsion production is enabled at an optimum quantity ofproduction scale corresponding to a required production quantity.

[0323] Third, the production apparatus of the silver halide photographicemulsion as described above in the first or the second is constitutedsuch that a micro heat exchanger is connected so that the reactionsolution processed by the nucleus forming reaction and two-liquid mixingmicroreactor or the nucleus forming reaction and three-liquid mixingmicroreactor is introduced therein, the reaction solution introduced tothe micro heat exchanger is cooled at a rate of 5° C. or more perminutes, preferably 10° C. or more per minute, more preferably 20° C. ormore per minute, still more preferably 40° C. or more per minute, and aripening reaction of nuclei in the reaction solution is stopped.

[0324] By the constitution as described above, the ripening reaction ofthe nuclei in the reaction solution is stopped by the micro heatexchanger, so that the generated nuclei become only those having adesired single crystal structure, the size distribution of the nucleusgrains is made narrow, and the size and number of the nucleus grains aremade uniform. Further, in the microreactor, the diffusion rate isincreased by raising the temperature of the process liquid to lessen atime difference between the start of ion diffusion in the vicinity ofthe interface where two liquids are in contact with each other and theend of diffusion of an ion placed at the furthest place from thisinterface, and a more uniform reaction product can be obtained.Furthermore, in the inside of the microreactor, the process solution isheated up to a predetermined temperature by the temperature controlmeans, the diffusion rate of the silver ion and the halogen ion isincreased to the required rate, and the nucleus forming process isprecisely and efficiently performed. Here, the reaction of the silverion and the halogen ion is a reaction that is performed at a very highrate, and they react in the order of millisecond. On the other hand, inthe Ostwald ripening, there arises such a ripening reaction that formedfine grains are molecule-dissolved and are merged in larger grains (hostgrain), and it is assumed that the reaction rate is slower than that ofthe ion reaction by approximately one order. Thus, in the microreactor,the process solution is heated by the temperature control means, so thatthe nucleus forming reaction is accelerated, and a fine-grain formationtime by diffusion is shortened, and a time from the start of the firstreaction to the end of the final reaction can be made short. Here,although the Ostwald ripening also proceeds, since the reaction speed isslow, by performing a cooling process in which the liquid is sent to themicro heat exchanger at the point of time when the reaction in thenucleus forming reaction and grain growth reaction microreactors hasbeen completed, and the temperature of the process liquid is quicklylowered, it becomes possible to suppress the apparent reaction of theOstwald ripening. In this way, the difference between the reaction rateof the silver ion and the halogen ion and the reaction rate of theOstwald ripening is effectively utilized, and the process of the nucleusforming reaction and the grain growth reaction can be performedprecisely and efficiently.

[0325] Fourth, in the production apparatus of the silver halidephotographic emulsion as described in one of the first to the third, thetemperature control means or the micro heat exchanger is constituted toenable heating such that within five seconds, a diffusion rate becomes adiffusion rate 1.1 times or more as high as a diffusion rate at atemperature before the reaction of a reactive ion.

[0326] By the constitution as described above, in the inside of thenucleus forming reaction and two-liquid mixing microreactor or thenucleus forming reaction and three-liquid mixing microreactor, thediffusion rates of the silver ions and the halogen ions are respectivelyincreased to the required rates, and the silver halide nucleus formingreaction is accelerated so that the silver ions and the halogen ions areefficiently bonded to form nuclei, and the silver halide nucleus formingreaction can be controlled to enable efficient production.

[0327] (Fifth Embodiment)

[0328]FIG. 10 is a schematic view of a nucleus forming reaction andphysical ripening reaction microreactor 88 (corresponding to the processof the microreactor A30 and the heat exchanging microreactor A32 ofFIG. 1) for performing a nucleus forming process in grain formation of asilver halide emulsion in a pre-ripening process concerning a productionapparatus of silver halide photographic emulsion of the invention, andfor starting a subsequent physical ripening process.

[0329] The nucleus forming reaction and physical ripening reactionmicroreactor 88 are constituted as a three-liquid mixing microreactor.Incidentally, it may be constituted as a two-liquid mixing microreactor.

[0330] Here, the nucleus forming reaction and physical ripening reactionmicroreactor 88 is formed such that a first flow passage for leading asilver salt solution (fluid 1), a second flow passage for leading ahalide solution (fluid 2), and a third flow passage for leading water oran aqueous protective colloid solution (fluid 3) as an intermediatelayer for preventing the silver salt solution and the halide solutionfrom immediately coming in contact with each other, are formed, andparts of the adjacent ones of these three flow passages come in contactwith each other.

[0331] Further, the nucleus forming reaction and physical ripeningreaction microreactor 88 is constituted as such a device that thesethree fluids 1, 2 (the silver salt solution and the halide solution)substantially form thin layers, respectively, open interfaces are formedbetween adjacent ones of the fluids 1, 2 and 3 (the silver saltsolution, the halide solution, and the water or the aqueous protectivecolloid solution), the thicknesses of the thin layers of these threefluids 1, 2 and 3 (the silver salt solution, the halide solution, andthe water or the aqueous protective colloid solution) become 1 to 900 μmin the normal direction of the contact interface, a silver ion and ahalogen ion diffuse and move to the intermediate layer of the water orthe aqueous protective colloid solution provided between the silver saltsolution and the halide solution, and the silver ion and the halogen ionreact with each other, so that the silver halide grains are continuouslygenerated.

[0332] In the nucleus forming reaction and physical ripening reactionmicroreactor 88, since the nucleus formation is performed while the flowof the laminar flow occurs in one direction, the so-called localrecycling in which nuclei circularly flow does not occur. Thus, when thenucleus formation is performed, it is possible to prevent the occurrenceof such a state that the local recycling occurs in which the once formednuclei circularly flow and the unexpected growth occurs.

[0333] In this nucleus forming reaction and physical ripening reactionmicroreactor 88, the silver halide grains are made to diffuse into thewater or the aqueous protective colloid solution. That is, the water orthe aqueous protective colloid solution intervenes between the nucleusgrains formed by the nucleus forming reaction to extend the distancebetween the nucleus grains.

[0334] As stated above, in the nucleus forming reaction and physicalripening reaction microreactor 88, since the distance between thenucleus grains is instantaneously extended immediately after the nucleusforming reaction, the nucleus forming reaction and the grain growthreaction are separated so that the nucleus forming reaction and thegrain growth reaction do not simultaneously occur, the nucleus grains ofsilver halide emulsion formed by the nucleus forming reaction areformed, and can be suitably guided to the process for causing the graingrowth reaction at a subsequent stage.

[0335] The nucleus forming reaction and physical ripening reactionmicroreactor 88 is constituted to include temperature control means 89capable of performing the temperature control of an objective fluid byperforming a heat exchange between the objective fluid introduced insideand a separately introduced temperature control medium.

[0336] This temperature control means 89 may be constituted such thatthe whole device of the nucleus forming reaction and physical ripeningreaction microreactor 88 is housed in a container whose temperature iscontrolled.

[0337] Further, the temperature control means 89 may perform a thermalcycle in such a way that a heater structure of a metal resistance wire,polysilicon or the like is formed in the device of the nucleus formingreaction and physical ripening reaction microreactor 88, this is usedfor heating, and natural cooling is used for cooling.

[0338] With respect to the sensing of temperature, in the case of themetal resistance wire, the same resistance wire as the heater is formed,and temperature detection is performed on the basis of the change of theresistance value, and in the case of the polysilicon, a thermocouple isused to perform detection.

[0339] With respect to the temperature control means 89, a Peltierelement is mounted in the nucleus forming reaction and physical ripeningreaction microreactor 88 so that the element is brought into contactwith the reactor, and heating and cooling may be performed from theoutside. A temperature control method is selected in accordance with ause and a material of the body of the nucleus forming reaction andphysical ripening reaction microreactor 88.

[0340] In order to increase the diffusion rate of the silver ion and thehalogen ion in the nucleus forming reaction and physical ripeningreaction microreactor 88, a structure is adopted to be capable of givingsuch a temperature that the diffusion rate of the silver ion and thehalogen ion becomes 1.1 times or more, preferably 1.5 times or more ashigh as the diffusion rate at a temperature of a liquid supplied to areaction portion in the nucleus forming reaction and physical ripeningreaction microreactor 88.

[0341] That is, the structure is adopted to enable heating so thatwithin five seconds, the diffusion rate becomes 1.1 times or more ashigh as the diffusion rate at the temperature before the reaction of areactive ion.

[0342] Further, in the nucleus forming reaction and physical ripeningreaction microreactor 88, the temperature control means 89 isconstituted by a micro heat exchanger capable of transmitting heat sothat the temperature of the liquid supplied to the reaction portion isincreased at a rate of 5° C. or more per minute, preferably 10° C. ormore per minute, more preferably 20° C. or more. In addition, the microheat exchanger is constituted such that a heat exchange range is set sothat a length of a time obtained by dividing a volume (Vh) calculatedfrom a length and depth of a microchannel by a flow volume becomes 5times or less, preferably 2 times or less as long as a diffusion time(td) at the temperature of the liquid supplied to the microreactor andthe heat exchange can be made.

[0343] When the nucleus forming reaction and physical ripening reactionmicroreactor 88 and the temperature control means 89 are specificallyconstituted, conditions of specific numerical values and the like wheneach portion is constituted can be determined as described below.

[0344] In general, the diffusion rate is a function of concentration,temperature and the like. Various estimation methods are recited asestimation of a liquid layer diffusion coefficient in a paragraph oftransport property of Chemical Engineering Handbook.

[0345] In this book, there is Wilke-Chang expression described below, inwhich the diffusion coefficient is recited as an expression relating totemperature.

D ₁₂∞=2.946*10⁻¹¹ (βM _(r,2))^(1/2) T/(μ₂ V _(b,1) ^(0,6))

[0346] where,

[0347] D₁₂∞; infinite dilution concentration

[0348] M_(r,2); molecular weight of diffusion medium

[0349] V_(b,1); mole volume of liquid layer at standard boiling point

[0350] β; association factor of diffusion medium

[0351] T; temperature

[0352] μ; liquid viscosity.

[0353] As indicated in this Wilke-Chang expression, the diffusioncoefficient relates to the temperature, and the diffusion rate can beimproved by raising the temperature.

[0354] In the microreactor, in the case where channels having the samelength are used, it is possible to increase throughput by widening thechannel width. Thus, by using the relation of the Wilke-Changexpression, under the condition that the channel width is made constant,the diffusion rate is improved by raising the temperature, and it ispossible to decrease a difference in time between the start of diffusionof an ion in the vicinity of the interface where two liquids are incontact with each other and the end of the diffusion of an ion at aplace remotest from this interface, and a more uniform reaction productcan be obtained.

[0355] Accordingly, in order to use the foregoing characteristic, it isadvantageous to use a structure so as to make the diffusion rate as highas possible.

[0356] As stated above, when a structure is used such that thetemperature control means 89 is provided in the nucleus forming reactionand physical ripening reaction microreactor 88, a silver halide nucleusformation and growth reaction can be controlled so that the diffusionrate of a silver ion and a halogen ion is increased to a required rateand the production can be precisely and efficiently made.

[0357] Next, a structural example shown in FIG. 11 in the fifthembodiment of the invention will be described. FIG. 11 is a schematicview of a nucleus forming reaction and physical ripening reactionmicroreactor 88 and a micro heat exchanger 90 in which in a pre-ripeningprocess concerning a production apparatus of silver halide photographicemulsion of the invention, a nucleus forming process in grain formationof a silver halide emulsion is performed and the growth of nuclei istemporarily stopped at a stage where a desired nucleus is formed so asto be guided to a next grain growth reaction.

[0358] The nucleus forming reaction and physical ripening reactionmicroreactor 88 is constituted to be equivalent to that shown in FIG.10.

[0359] The micro heat exchanger 90 is constituted as a microreactor forperforming a temperature control of changing a temperature of anintroduced process liquid to a predetermined temperature in the shortestpossible time, and is constituted similarly to the temperature controlmeans of the foregoing nucleus forming reaction and physical ripeningreaction microreactor 88.

[0360] The micro heat exchanger 90 is disposed to be connected in seriesto the nucleus forming reaction and physical ripening reactionmicroreactor 88, water or an aqueous protective colloid solution, intowhich silver halide grains are diffused, which is discharged from thenucleus forming reaction and physical ripening reaction microreactor 88,is introduced into the micro heat exchanger 90, and a temperaturecontrol (for example, a cooling process) is performed at a rate of 10°C. or more per minute, preferably 20° C. or more per minute, morepreferably 40° C. or more to stop the nucleus ripening reaction, so thatonly those having a desired single crystal structure exemplified inFIGS. 13A, 13B, 13C, 13D or 13E are obtained (the shapes of nucleusgrains are made uniform), the size distribution of the nucleus grains ismade narrow, and the size and number of the nucleus grains can be madeuniform.

[0361] That is, the micro heat exchanger 90 is constituted to have acooling rate of 5° C. or more per minute.

[0362] As stated above, in the case where the heating temperaturecontrol means is provided in the nucleus forming reaction and physicalripening reaction microreactor 88, and further, the micro heat exchanger90 is provided which receives the process liquid processed by thenucleus forming reaction and physical ripening reaction microreactor 88and can quickly cool it, for example, in the inside of the nucleusforming reaction and physical ripening reaction microreactor 88, theprocess liquid is heated to a predetermined temperature by thetemperature control means to increase the diffusion rate of the silverion and the halogen ion to a required rate, and the nucleus formingprocess is precisely and efficiently performed.

[0363] Here, the reaction of the silver ion and the halogen ion is areaction performed at a very high rate, and the silver ion and thehalogen ion react in the order of millisecond. On the other hand, in theOstwald ripening, there occurs such a ripening reaction that generatedfine grains are molecular-dissolved, and are merged by larger grains(host grain), and with respect to a reaction rate, it is presumed thatthe reaction is slower than the ion reaction by approximately one order.

[0364] Thus, in the nucleus forming reaction and physical ripeningreaction microreactor, the process liquid is heated by the temperaturecontrol means, so that the nucleus forming reaction is accelerated, afine-grain formation time by diffusion is accelerated, and a time fromthe start of a first reaction to the end of a final reaction can be madeshort.

[0365] Incidentally, here, although the Ostwald ripening reaction alsoproceeds, since the reaction rate is low, by performing a coolingprocess in which the liquid is sent to the micro heat exchanger 90 atthe point of time when the reaction in the nucleus forming reaction andphysical ripening reaction microreactor 88 is ended and the temperatureof the process liquid is quickly lowered, it becomes possible tosuppress the apparent reaction of the Ostwald ripening. In this way, thedifference between the reaction rate of the silver ion and the halogenion and the reaction rate of the Ostwald ripening is advantageouslyused, and the process of the nucleus forming reaction and the graingrowth reaction can be performed precisely and efficiently.

[0366] Next, a structural example shown in FIG. 12 in the fifthembodiment of the invention will be described. FIG. 12 is a schematicview of a nucleus forming reaction and physical ripening reactionmicroreactor 88, a micro heat exchanger 90, and a nucleus growingmicroreactor 92, in which the nucleus forming process in the grainformation of the silver halide emulsion is performed in the pre-ripeningprocess concerning the production apparatus of the silver halidephotographic emulsion of the invention, and at a stage where desirednuclei are formed, the growth of the nuclei are temporarily stopped, andthe subsequent grain growth reaction is continued.

[0367] The nucleus forming reaction and physical ripening reactionmicroreactor 88 is constituted to be equivalent to that shown in FIG.10. Further, the micro heat exchanger 90 is constituted to be equivalentto that shown in FIG. 11.

[0368] The nucleus growing microreactor 92 is constituted similarly tothe microreactor B34 shown in FIG. 1.

[0369] By the constitution as described above, by the same operation asthe above, nuclei are formed by the nucleus forming reaction andphysical ripening reaction microreactor 88, an emulsion subjected totemperature control (for example, cooling process) by the micro heatexchanger 90 is introduced into the nucleus growing microreactor 92, anew silver nitrate solution and halide solution are mixedsimultaneously, the Ostwald ripening is accelerated, nuclei of smallcrystals of silver halide grow into nuclei of middle sized crystals ofsilver halide, and it proceeds to a next process, and further, asubsequent process is continuously performed by using the microreactor,and the silver halide photographic emulsion can be produced.

[0370] The emulsion subjected to the temperature control (for example,cooling process) by the micro heat exchanger 90 is stored in anunillustrated growth reacting tank, and the silver halide photographicemulsion can be produced by a conventional batch production system.

[0371] In the subsequent process, since the growth reaction can beperformed from the nucleus grains having a desired single crystalstructure, the growth reaction becomes easy to perform, and the crystalshape and size distribution of the final grains can be made moreuniform.

[0372] Incidentally, since the structure, operation and effect of thefifth embodiment other than the above descriptions are the same as thoseof the first or third embodiment, the descriptions are omitted.

[0373] Next, a sixth embodiment of the invention will be described withreference to FIG. 14.

[0374] The gist of the sixth embodiment is as follows.

[0375] First, a production apparatus of silver halide photographicemulsion is constituted to perform a sensitizing process by amicroreactor including a mixing space in which in an open interfacewhere liquid chemicals for producing an emulsion introduced from a firstflow passage and containing dispersed nuclei of silver halide, and asolution introduced from a second flow passage and containing a materialhaving a low water solubility such as a dye are brought into contactwith each other and flow in a state of thin layers, the material havinga low water solubility such as the dye is diffused to be adsorbed by thenuclei of silver halide so that the sensitizing process is performed,and a temperature control means constituted to be capable of heating therespective liquids supplied to the mixing space from the respective flowpassages up to a temperature at which rapid mixing is performed.

[0376] By the constitution as described above, the respective nuclei(grains) of silver halide and the respective dye molecules meet andreact with each other under more uniform conditions, and the dyemolecules can be uniformly adsorbed by the surfaces of all nuclei ofsilver halide, so that heterogeneous adsorption at the time when theadded material having a low water solubility such as the dye is adsorbedby the surface of the silver halide grains can be prevented. Thus, inthe case where the sensitizing process is performed by using thismicroreactor, the silver halide photographic emulsion having uniformemulsion performance can be produced. Further, when the sensitizingprocess is performed by using this microreactor, the diffusion rates ofthe nuclei (grains) of silver halide and the dye molecules are increasedby heating, and the material having a low water solubility such as thedye can be efficiently adsorbed by the surface of the silver halidegrains. Furthermore, since the microreactor is used, a small productionsystem can be easily scaled up to a mass production system, and theemulsion production is enabled at an optimum quantity of productionscale corresponding to a required production quantity.

[0377] Second, a production apparatus of silver halide photographicemulsion is constituted such that a first flow passage for leadingliquid chemicals for producing an emulsion in which nuclei of silverhalide are dispersed, and a second flow passage for leading a solutioncontaining a material having a low water solubility such as a dye areprovided, parts of the two flow passages are jointed to form an openinterface between the fluids, the liquid chemicals for producing theemulsion and the solution containing the material having a low watersolubility are brought into contact with each other in a state wherethey form thin layers, respectively, the thicknesses of the thin layersof the liquid chemicals for producing the emulsion and the solutioncontaining the material having a low water solubility are made to be 10to 5000 μm, the length of the thin layers is made a length equivalent toa time 0.6 to 1 times as long as a time required for the material havinga low water solubility to diffuse in a length from an end to an end ofthe solution containing the material having a low water solubility at apredetermined flow and at a predetermined temperature of the dye, amicro heat exchanger is provided which can transfer heat to the liquidchemicals for producing the emulsion and the solution containing thematerial having a low water solubility, which come in contact with eachother in the state of the thin layers, at a rate of 5° C. or more perminute, preferably 10° C. or more per minute, more preferably 20° C. ormore per minute to improve the diffusion rate of a molecule such as thematerial having a low water solubility, and a sensitizing process isperformed by a microreactor for causing the material having a low watersolubility, such as the dye, diffused in the contact surface between theliquid chemicals for producing the emulsion and the solution containingthe material having a low water solubility to be adsorbed by the nucleiof silver halide.

[0378] By the constitution as described above, the respective nuclei(grains) of silver halide and the respective dye molecules meet andreact with each other under more uniform conditions, and the dyemolecules can be uniformly adsorbed by the surfaces of all nuclei ofsilver halide, so that the heterogeneous adsorption at the time when theadded material having a low water solubility such as the dye is adsorbedby the surface of the silver halide grain can be eliminated. Thus, inthe case where the sensitizing process is performed by using thismicroreactor, the silver halide photographic emulsion having uniformemulsion performance can be produced. Further, in the case where thesensitizing process is performed by using this microreactor, thediffusion rates of the nuclei (grains) of silver halide and the materialhaving a low water solubility are increased by quick heating using themicro heat exchanger, and the material having a low water solubilitysuch as the dye can be efficiently adsorbed by the surface of the silverhalide grain. Since the microreactor is used, a small production systemcan be easily scaled up to a mass production system, and the emulsionproduction is enabled by an optimum quantity of production scalecorresponding to a required production quantity.

[0379] Third, a production apparatus of silver halide photographicemulsion is constituted such that a first flow passage for leadingliquid chemicals for producing an emulsion in which nuclei of silverhalide are dispersed, and a second flow passage for leading a solutioncontaining a material having a low water solubility such as a dye areprovided, parts of the two flow passages are joined to form an openinterface between the fluids, and the liquid chemicals for producing theemulsion and the solution containing the material having a low watersolubility are brought into contact with each other in a state wherethey form thin layers, respectively, and plural channels are formed sothat the thicknesses of the thin layers of the liquid chemicals forproducing the emulsion and the solution containing the material having alow water solubility become 10 to 5000 μm, the liquid chemicals forproducing the emulsion and the solution containing the material having alow water solubility are made to flow into each of the channels at apressure and a flow rate so that the respective flow rates become equalto each other, forcible mixing means is provided in a mixing space wherethey are brought into contact with each other after the flow is adjustedfor 1 second or more, and a sensitizing process is performed by amicroreactor in which the liquid chemicals for producing the emulsionand the solution containing the material having a low water solubilitysuch as the dye are forcibly mixed, so that the dispersed materialhaving a low water solubility, such as the dye, is adsorbed by thenuclei of silver halide.

[0380] By the constitution as described above, the respective nuclei(grains) of silver halide and the respective dye molecules meet andreact with each other under more uniform conditions, and the dyemolecules can be adsorbed by the surface of all nuclei of silver halide,so that heterogeneous adsorption at the time when the added materialhaving a low water solubility such as the dye is adsorbed by the surfaceof the silver halide grain can be eliminated. Thus, in the case wherethe sensitizing process is performed by using this microreactor, thesilver halide photographic emulsion having uniform emulsion performancecan be produced. Further, in the case where the sensitizing process isperformed by using this microreactor, the diffusion rates of the nuclei(grains) of silver halide and the material having a low water solubilityare increased by quick mixing using the forcible mixing means, so thatthe material having a low water solubility such as the dye can beefficiently adsorbed by the surface of the silver halide grain.Moreover, since the microreactor is used, a small production system canbe easily scaled up to a mass production system, and the emulsionproduction is enabled at an optimum quantity of production scalecorresponding to a required production quantity.

[0381] (Sixth Embodiment)

[0382]FIG. 14 is a schematic view of a spectral sensitizing processingmicroreactor 94 for performing a spectral sensitizing process (processin which a material having a low water solubility such as a sensitizingdye is added to adjust a light absorption wavelength) of a silver halideemulsion in an after-ripening process concerning a production apparatusof silver halide photographic emulsion of the invention.

[0383] The spectral sensitizing processing microreactor 94 can beconstituted by using a general two-liquid mixing microreactor.

[0384] Here, the spectral sensitizing processing microreactor 94 isformed such that a first flow passage for leading liquid chemicals forproducing an emulsion (fluid 1) in which a nuclei of silver halide aredispersed, and a second flow passage for leading a solution containing amaterial having a low water solubility such as a dye (solution in whicha sensitizing dye is dissolved in methanol, etc.) (fluid 2) are formed,and parts of these two flow passages come in contact with each other.

[0385] Further, the spectral sensitizing processing microreactor 94 isconstituted such that these two fluids 1 and 2 (the liquid chemicals forproducing the emulsion in which the nuclei of silver halide aredispersed and the solution containing the material having a low watersolubility such as a dye) substantially form thin layers, respectively,and an open interface is formed between the adjacent fluids.

[0386] The spectral sensitizing processing microreactor 94 isconstituted such that the thicknesses of these two thin layers are made10 to 5000 μm per layer, and the lengths of the two thin layers arerespectively made a length equivalent to a time 0.6 to 1 times as longas a time required for the material having a low water solubility suchas the dye, to diffuse from an end to the other end of the fluid 1 at apredetermined flow rate and at a predetermined temperature.

[0387] In this manner, at the interface formed by the solution forproducing silver halide emulsion and the solution containing thematerial having a low water solubility such as the dye, the sensitizingdye is made to be adsorbed by the nuclei of silver halide by mutualdiffusion from the contact interface, so that the sensitizing reactionis continuously caused.

[0388] As a method of adding a dye for the spectral sensitizing processof the silver halide emulsion in the after-ripening process, there are amethod of using a solution in which a dye is dissolved in a solvent, anda method of using a solution containing a dye solid dispersion, and thespectral sensitizing processing microreactor 94 can used for both themethods.

[0389] Further, in the spectral sensitizing processing microreactor 94,in order to improve the diffusion rate of the dye molecule, a micro heatexchanger 96 as temperature control means is installed which can performa temperature control to transfer heat at a rate of 5° C. or more perminute, preferably 10° C. or more per minute, more preferably 20° C. ormore to the liquid chemicals for producing the emulsion in which thenucleus of silver halide is dispersed and the solution containing thematerial having a low water solubility such as the dye, which areintroduced in the spectral sensitizing processing microreactor 94 andare allowed to react to each other.

[0390] In addition, the spectral sensitizing processing microreactor 94is constituted such that in each of the first flow passage for leadingthe liquid chemicals for producing the emulsion (fluid 1) in which thenuclei of silver halide are dispersed and the second flow passage forleading the solution containing the material having a low watersolubility such as the dye (solution in which the sensitizing dye isdissolved in methanol, etc.) (fluid 2), a straightening field isprovided at a predetermined portion on each of the flow passages frominlets for introducing the fluid 1 and the fluid 2 to a position wherethe fluid 1 and the fluid 2 come in contact with each other at parts ofthe two flow passages, a straightening structure 100 is provided in thestraightening filed, which adjusts the flow for one second or more in astate where the thicknesses of the thin layers in the respective flowpassages are 10 to 5000 μm per layer in the vertical direction and thefluids are made to flow in plural channels at a pressure and a flowvolume so that the respective flow rates become equal to each other, andthe two fluids are brought into contact with each other at a place wherethe flows are straightened by the straightening structure 100.

[0391] In addition, in the spectral sensitizing processing microreactor94, a mixing space is provided at the place where the parts of the twoflow passages come in contact with each other and the open interface isformed, and forcible mixing means 98 is installed in the mixing space,which gives mechanical energy, such as ultrasonic sound or ultra highfrequency vibration, or electric energy, such as electromagnetic wave,for rapidly mixing the liquids supplied from the respective flowpassages and quickly mixes the fluids to allow the dye to be adsorbed bythe respective nuclei of silver halide.

[0392] The micro heat exchanger 96 installed in the spectral sensitizingprocessing microreactor 94, may be constituted to be disposed in one ofor both of the straightening field provided in each of the flow passagesand for adjusting the flow, and the mixing space for rapidly mixing theliquids supplied from the respective flow passages, so that heat istransferred to the introduced liquids at a rate of 5° C. or more perminute, preferably 10° C. or more per minute, more preferably 20° C. ormore per minute to enable temperature control, and more precisetemperature control may be enabled.

[0393] Further, the spectral sensitizing processing microreactor 94 maybe constituted such that in order to increase places where the nuclei ofsilver halide in the liquid chemicals for producing the emulsion and thematerial having a low water solubility such as the dye meet each other,plural mixing spaces in the spectral sensitizing processing microreactor94 are provided in parallel, and the process quantity can be furtherimproved.

[0394] In the spectral sensitizing processing microreactor 94constituted as stated above, the liquid chemicals for producing theemulsion in which the nuclei of silver halide are dispersed isintroduced from the first flow passage, the solution containing thematerial having a low water solubility such as the dye is introducedfrom the second flow passage, these liquids are respectively made thestraightened flows by the straightening structure 100, the temperaturecontrol is performed by the micro heat exchanger 96, and the respectiveliquids having the predetermined temperature are rapidly mixed by theforcible mixing means 98, so that the respective silver halide grainsand the respective dye molecules meet and react with each other undermore uniform conditions, and the dye molecules can be uniformly adsorbedby the surfaces of all silver halide grains, and accordingly,heterogeneous adsorption at the time when the added material having alow water solubility such as the dye is adsorbed by the surface of thesilver halide grain can be eliminated.

[0395] Although heterogeneous adsorption appears in the reaction of theconventional macro mixing, for example, the dye or the like is adsorbedby the silver halide grains in multilayer adsorption, the dye or thelike is adsorbed by the silver halide grain in monolayer adsorption, andthe dye or the like is not adsorbed by the silver halide grains, it ispossible to prevented the heterogeneous adsorption by this embodiment,and it is possible to prevent the photographic performance from beingchanged by, for example, the occurrence of rearrangement of the dye orthe like adsorbed by the silver halide grains during preservation.

[0396] In addition, since the dye molecules can be equally adsorbed bythe surfaces of all silver halide grains, it is not necessary to add anexcessive number of dye molecules to a predetermined number of silverhalide grains to eliminate silver halide grains by the surface on whicha dye molecule is not adsorbed, and a suitable number of dye moleculeshave only to be added, and accordingly, the quantity of material havinga low water solubility, such as an expensive dye, consumed can bereduced and the production cost can be reduced.

[0397] That is, in the case where the spectral sensitizing process isperformed by using the mixing microreactor to simultaneously mix theliquid chemicals for producing the emulsion in which the nuclei (grains)of silver halide are dispersed in the aqueous protective colloidsolution and the spectral sensitizing agent as the solution in which thespectral sensitizing dye is dissolved in methanol, when viewedmicroscopically, since one layer of molecules of the spectralsensitizing agent can be uniformly adsorbed by the surface of the singlenucleus (grain) of silver halide, the suitable spectral sensitizingprocess can be performed.

[0398] Thus, in the case where the mixing microreactor is used toexecute the spectral sensitizing process, it is possible to prevent thegeneration of the nucleus (grain) of silver halide by which the spectralsensitizing molecules are not adsorbed, to prevent the formation of thenucleus (grain) of silver halide on which spectral sensitizing moleculesare excessively adsorbed (multilayer absorption state in which themolecules of the spectral sensitizing agent are adsorbed on the surfaceof the nucleus (grain) of silver halide to form a multilayer), or toprevent the spectral sensitizing molecule from remaining, and it ispossible to prevent the spectral sensitizing agent from being wasted.

[0399] Further, in the case where the reaction was performed by usingthe spectral sensitizing processing microreactor 94 concerning the sixthembodiment, it was confirmed that the adsorption of the material havinga low water solubility such as the dye, onto the silver halide grainbecomes stronger. It was also confirmed that the storage property in arefrigerator and the storage property after being molten of the thusproduced silver halide emulsion were remarkably improved.

[0400] Incidentally, since the structure, operation and effect of thesixth embodiment other than the above descriptions are the same as thoseof the first or the third embodiment, the descriptions are omitted.

[0401] Next, a seventh embodiment of the invention will be describedwith reference to FIGS. 15 to 18.

[0402] The gist of the seventh embodiment is as follows.

[0403] First, a production apparatus of silver halide photographicemulsion is constituted to be a microreactor including plural liquidincoming ports for a first process liquid and liquid incoming ports fora second process liquid, which are formed on one chip and arealternately disposed at equal intervals, and reaction portions formed onthe one chip, one end of each of which is connected to the liquidincoming port of the first process liquid and the adjacent liquidincoming port of the second process liquid, and the other end of each ofwhich is connected to a liquid outgoing port, the reaction portionsbeing formed into microchannels in each of which the fluidssubstantially form thin layers, an open interface is formed between theadjacent liquids, and the liquids are mixed by diffusion and movement,and the number of the reaction portions being equal to the number of theliquid incoming ports of the first process liquid or the adjacent liquidincoming ports of the second process liquid.

[0404] By the constitution as described above, mixing is performed bythe diffusion and movement in the plural reaction portions formed on theone chip, so that a scale can be increased to be capable of processingthe liquid in large quantities, and a construction can be made torealize an optimum quantity of production scale corresponding to arequired production quantity.

[0405] Second, a production apparatus of silver halide photographicemulsion is constituted to be a microreactor including a liquid incomingport for a first process liquid, a liquid incoming port for a secondprocess liquid, and a liquid incoming port for a third process liquid,which are formed on one chip, and a reaction portion formed on the onechip, one end of which is connected to the liquid incoming port of thefirst process liquid, the liquid incoming port of the second processliquid, and the liquid incoming port of the third process liquid, andthe other end of which is connected to a liquid outgoing port, thereaction portion being formed into a microchannel in which the fluidssubstantially form thin layers, an open interface is formed between theadjacent liquids, and the liquids are mixed by diffusion and movement.

[0406] By the foregoing structure, the mixing of three kinds of processliquids by diffusion and movement can be performed in the singlereaction portion formed on the one chip, and by providing plural suchchips in parallel, a scale can be increased so as to be capable ofprocessing the liquid in large quantities, and a construction can bemade to realize an optimum quantity of production scale corresponding toa required production quantity.

[0407] Third, a production apparatus of silver halide photographicemulsion is constituted to be a microreactor including plural liquidincoming ports of a silver salt solution and plural liquid incomingports of a halide solution, which are formed on one chip and arealternately disposed at equal intervals, and reaction portions formed onthe one chip, one end of each of which is connected to the liquidincoming port of the silver salt solution and the adjacent liquidincoming port of the halide solution, and the other end of each of whichis connected to a liquid outgoing port, the reaction portions beingformed into microchannels in each of which the fluids substantially formthin layers, an open interface is formed between the adjacent liquids, asilver ion and a halogen ion diffuse and move, and the silver ion andthe halogen ion react with each other to continuously generate a nucleusof silver halide, and the number of the reaction portions being equal tothe number of the liquid incoming ports of the silver salt solution orthe adjacent liquid incoming ports of the halide solution.

[0408] By the constitution as describe above, the silver ions and thehalogen ions simultaneously diffuse and move in the plural reactionportions formed on the one chip, and the silver ions and the halogenions react so that the nuclei of silver halide can be continuouslyformed, and accordingly, a scale can be increased so as to be capable ofprocessing the solutions in large quantities, and a construction can bemade to realize an optimum quantity of production scale corresponding toa required production quantity.

[0409] Fourth, a production apparatus of silver halide photographicemulsion is constituted to be a microreactor including a liquid incomingport for a silver salt solution, a liquid incoming port of water orprotective colloid solution, and a liquid incoming port for a halidesolution, which are formed on one chip, and a reaction portion formed onthe one chip, one end of which is connected to the liquid incoming portof the silver salt solution, the liquid incoming port for the water orthe aqueous protective colloid solution, and the liquid incoming portfor the halide solution, and the other end of which is connected to aliquid outgoing port, the reaction portion being formed into amicrochannel in which a thin layer of the silver salt solution and athin layer of the halide solution are disposed at both sides of a thinlayer of the water or the aqueous protective colloid solution as anintermediate layer, open interfaces are formed between the adjacent thinlayers of these three liquids, a silver ion and a halogen ion diffuseand move between these three thin layers, the silver ion and the halogenion are made to react with each other while progress of Ostwald ripeningis controlled by the water or the aqueous protective colloid solution,and a silver halide grain is continuously formed.

[0410] By the constitution as described above, the silver ion and thehalogen ion are made to react with each other in the single reactionportion formed on the one chip while the progress of the Ostwaldripening is controlled by the water or the aqueous protective colloidsolution, so that the process of continuously forming the silver halidegrain can be performed, and by providing plural such chips in parallel,a scale can be increased so as to be capable of processing the solutionin large quantities, and a construction can be made to realize anoptimum quantity of production scale corresponding to a requiredproduction quantity.

[0411] (Seventh Embodiment)

[0412]FIG. 15 is a schematic view exemplifying a reaction tank devicefor performing a nucleus forming process in grain formation of a silverhalide emulsion in a pre-ripening process concerning a productionapparatus of silver halide photographic emulsion of the invention.

[0413] As shown in FIG. 15, this reaction tank device uses a tank 102 asa reaction container (it may be a reaction tank for performing graingrowth). This tank 102 is constituted as a batch type reaction containerdevice provided with an agitator capable of processing a fixed largequantity, for example, 1000 1 (1 t) of liquid at a time.

[0414] An agitation vane 106 to be rotatively driven by the rotationdriving force of a motor 104 is installed in the tank 102 to agitate asolution filled in the inside of the tank.

[0415] A temperature control means 108 for heating or cooling thereaction solution is disposed on the outer peripheral surface of thetank 102 to perform a temperature control of the solution filled in theinside of the tank. The temperature control means 108 is constituted byusing a means for heating or cooling by causing a heat exchange medium(water, water vapor, liquid organic material, flame gas, etc.) to flowthrough a temperature control part, or a means for performing atemperature control by installing an element for electrically heating orcooling in the temperature control part.

[0416] The tank 102 is connected to a flow passage 112 for supplying,from its upper part, water or protective colloid solution in whichnuclei of small crystals of silver halide formed by a nucleus formingprocessing microreactor 110 are dispersed.

[0417] The nucleus forming processing microreactor 110 for supplying theliquid in which the nuclei of the small crystals of silver halide aredispersed is constituted as a two-liquid mixing microreactor as shown inFIGS. 16 or 17 or a three-liquid mixing microreactor shown in FIG. 18.

[0418] A two-liquid mixing microreactor 110A shown in FIG. 16 isconstituted as a microreactor chip having a Y-shaped groove and forperforming a reaction of two liquids.

[0419] The two-liquid mixing microreactor 110A is constituted such thata liquid incoming port 114 and a liquid incoming port 116 are providedat tip ends of forked grooves having a Y shape, and a liquid outgoingport 118 is provided at a tip end of one extending groove of the Yshape.

[0420] In the two-liquid mixing microreactor 110A, a portion from theone liquid incoming port 114 to an intersection of the Y shape is made afirst flow passage for leading a silver salt solution (silver nitratesolution) (fluid 1), and the other liquid incoming port 116 to theintersection of the Y shape is made a second flow passage for leading ahalide solution (fluid 2).

[0421] In the two-liquid mixing microreactor 110A, a portion from theintersection of the Y shape to the tip end of the one extending grooveis made a reaction portion (microchannel) where parts of the first flowpassage and the second flow passage come into contact with each other,the two fluids substantially form thin layers here, an open interface isformed between these two fluids, the thicknesses of these two thinlayers is 1 to 900 μm per layer in the normal direction of the contactinterface, preferably 1 to 300 μm, reactive substances (ion, monomer,etc.), for example, a silver ion and a halogen ion diffuse and movebetween these two thin layers, and the silver ion and the halogen ionreact with each other, so that the silver halide grains are continuouslyformed.

[0422] By using a plurality of the two-liquid mixing microreactors 110Asimultaneously, a scale is increased and a structure having requiredprocessing capacity is obtained.

[0423] A two-liquid mixing microreactor 110B shown in FIG. 17 isconstituted so as to increase process capacity as the need arises.

[0424] The two-liquid mixing microreactor 110B is constituted such thatas shown in the drawing, a liquid incoming port 114 for a silver saltsolution and a liquid incoming port 116 for a halide solution arealternately disposed at equal intervals, and a first flow passage and asecond flow passage are disposed to be in parallel with each other.

[0425] The two-liquid mixing microreactor 110B is constituted such thatexcept for the first flow passage or the second flow passage at bothends, each of the intermediate first flow passage and second flowpassage forks into two branches, each of which is connected to areaction portion (microchannel) from an intersection of a Y shape to atip end of one extending groove.

[0426] By combining the Y-shaped grooves as stated above, the processingcapacity can be increased as the need arises, and the two-liquid mixingmicroreactor 110B that has an integral structure as a whole and isscaled up, can be constituted.

[0427] Next, as shown in FIG. 18, a three-liquid mixing microreactor110C that can constitute a system for allowing two reactive liquids toreact with each other, will be described.

[0428] The three-liquid mixing microreactor 110C shown in FIG. 18 isconstituted as a microreactor chip for performing a reaction of threeliquids by providing a liquid incoming port 114, a liquid incoming port116, and a liquid incoming port 120 at respective tip end parts ofinverted E-shaped and three-forked grooves formed at one end part asshown in the drawing, and by providing a liquid outgoing port 118 at atip end part of one groove extending toward the other end part of theinverted E shape.

[0429] In the three-liquid mixing microreactor 110C, a portion from theone liquid incoming port 114 to an inverted E-shaped intersection ismade a first flow passage for leading a silver salt solution (silvernitrate solution) (fluid 1), a portion from the other liquid incomingport 116 to the inverted E-shaped crossing place is made a second flowpassage for leading a halide solution (fluid 2), and a portion from theliquid incoming port 120 lying midway between them to the invertedE-shaped intersection is made a third flow passage for leading water oran aqueous protective colloid solution (protective colloid solutiontypified by gelatin or agar) as an intermediate layer for preventingboth the first and second fluids from immediately coming in contact witheach other and for stabilizing a reaction product formed by the reactionof these two fluids.

[0430] The three-liquid mixing microreactor 110C is constituted suchthat a portion leading to the tip end part of the groove extendingtoward the other end of the inverted E shape is made a reaction portion(microchannel) where parts of the first flow passage, the second flowpassage, and the third flow passage come in contact with each other, thethree fluids substantially form thin layers here, open interfaces areformed between the adjacent ones of these three fluids, the thicknessesof these three thin layers are 1 to 900 μm per layer in the normaldirection of the contact interface, a reactive substance (ion, monomer,etc.), for example, a silver ion and a halogen ion diffuse and movebetween these three thin layers, and the silver ion and the halogen ionreact with each other while the progress of the Ostwald ripening iscontrolled by the water or the aqueous protective colloid solution, sothat a silver halide grain is continuously formed.

[0431] The three-liquid mixing microreactor 110C is constituted suchthat plural reaction spaces (reaction portions) are provided in onestructure, or a required number of microreactors are simultaneouslyused, so that a scale is increased, and necessary processing capacity isobtained.

[0432] Next, the outline of a method of forming the two-liquid mixingmicroreactor 110A, the two-liquid mixing microreactor 110B or thethree-liquid mixing microreactor 110C constituted as described abovewill be described. In the microreactor 110A, 110B or 110C, silicon (Si)or glass can be used for the material.

[0433] For example, when the microreactor 110A, 110B or 110C isconstituted by using PDMS (polydimetylslloxane) as a kind of siliconerubber, it can be relatively easily formed when a method called softlithography is used.

[0434] In the soft lithography, a microstructure patterned by a normalphotolithographic process in advance is used as a mold to performmolding, and a PDMS microchip is fabricated.

[0435] Further, the PDMS microchip in which the microstructure is formedin this way is bonded onto a substrate, such as a flat acrylic plate, inwhich a required liquid incoming port and liquid outgoing port are boredin advance, and the microreactor 110A, 110B or 110C is constituted.

[0436] The microreactor 110A, the two-liquid mixing microreactor 110B,or the three-liquid mixing microreactor 110C can also be fabricated byusing glass as a raw material and by a normally used LIGA method.

[0437] A micro heat exchanger is installed in the microreactor 110A,110B or 110C.

[0438] The micro heat exchanger is constituted as, for example, acooling mechanism including a flow passage which is disposed to beadjacent to a microchannel to allow a reaction solution to flow in themicroreactor 110A, 110B or 110C and in which a heat medium flows, andprecisely perform a temperature control so that respective liquidsbefore reaction, reaction solutions, and liquids after completion ofreaction rapidly come to have a predetermined temperature.

[0439] When the microreactor 110A, 110B or 110C and the reaction tankdevice are used to perform the nucleus forming process or nucleusgrowing process in the grain formation of the silver halide emulsion inthe pre-ripening process in the production process of the silver halidephotographic emulsion, respective supply rates of a halide solution anda silver nitrate solution are controlled by measuring pAg values ofliquids during reaction or after the end of the reaction of a halidesolution and a silver nitrate solution in the microreactor 110A, 110B or110C, and the pAg value at the time of formation of the silver halidegrain are controlled, alternatively, pH values of liquids during thereaction of the halide solution and the silver nitrate solution or afterthe end of the reaction are measured, and the pH values of the fluidsare controlled so that the pH value at the time of the reaction becomesconstant, and as a result, the production operation can be automated.

[0440] Incidentally, since the structure, operation and effect of theseventh embodiment other than the above descriptions are the same asthose of the first or third embodiment, the descriptions are omitted.

EXAMPLES

[0441] Next, a description will be given of a specific example of thecase where the nucleus forming process or the nucleus growing process inthe grain formation of the silver halide emulsion in the pre-ripeningprocess in the production process of the silver halide photographicemulsion is performed using the microreactor 110A, 110B or 110C and thereaction tank device constituted as described above.

[0442] In this example, silver bromo-iodide tabular grains are preparedby using the microreactor 110A, 110B or 110C and the reaction tankdevice.

[0443] In this example, there are described a case of a comparativeexample using a mixer (volume in the mixer is 0.5 ml) shown in FIG. 1 ofJP-A No. 10-239787 in a system shown in FIG. 2 of JP-A No. 10-239787,and an example in which instead of this mixer, the foregoingmicroreactor 110A, 110B and 110C is used and tabular grains are preparedin a manner described below.

Comparative Example

[0444] (Emulsion 1-A)

[0445] A reaction container was made empty in advance, and 500 ml of0.021 M aqueous silver nitrate solution and 500 ml of 0.028M aqueous KBrsolution containing 0.1 mass % of low molecular weight gelatin (averagemolecular weight 40,000) were continuously added for 20 minutes into amixer (volume in the mixer was 0.5 ml) as shown in FIG. 1 of JP-A No.10-239787, a resultant emulsion was continuously poured into thereaction container for 20 minutes, and 1,000 ml of a fine-grain emulsionwas obtained. The revolving speed for agitation at that time was 2,000rpm.

[0446] (Nucleus Formation)

[0447] 300 ml of 10% bone gelatin solution in which 95% of amino groupswas phthalated and KBr were added to the emulsion to make the pBr valueof the emulsion in the reaction container to 2.1, and thereafter, thetemperature was raised to 75° C. and it was permitted to stand for 5minutes.

[0448] (Ripening)

[0449] Thereafter, 600 ml of 1.0 M silver nitrate solution, 600 ml of0.99 M KBr containing KI in an amount of 3 mol %, and 800 ml of 5% lowmolecular weight gelatin solution were added the mixer at a constantflow rate for 60 minutes. The fine-grain emulsion thus formed by themixer was continuously added into the reaction container. At that time,the revolving speed for agitation of the mixer was 2,000 rpm.

[0450] (Grain Growth)

[0451] During the grain growth, at the point of time when 70% of silvernitrate was added, IrC₆ was added in an amount of 8×10⁻⁸ mol/mol Ag anddoped. Further, before the end of the grain growth, a solution of yellowprussiate of potash was added into the mixer. The yellow prussiate ofpotash was doped in 3% (in terms of added silver) of shell parts of thegrains at a local concentration of 3×10⁻⁴ mol/mol Ag. After theaddition, the emulsion was cooled to 35° C., and was washed by a normalflocculation method, 70 g of lime processed bone gelatin was added anddissolved, and adjusted pAg value to 8.7 and pH value to 6.5, and then,the emulsion was preserved in a cold dark place. Table 1 showsproperties of the tabular grain prepared and obtained by theconventional method.

Content of this Example

[0452] (Emulsion 1-B)

[0453] Except that nucleus formation was changed as described below, theemulsion was prepared in the same way as the emulsion 1-A of thecomparative example.

[0454] As a mixer, a microreactor made of glass and illustrated in FIG.16 is fabricated by the LIGA method, which has such a configuration thatflow passages each having a flow passage having a width of 200 μm and adepth of 200 μm, from which a halide solution and a silver nitratesolution flow and are supplied, and a plurality of the reactors areprovided to constitute a process system capable of continuously formingfine grains similar to the comparative example.

[0455] In this process system, a micro heat exchanger was used at theexit of the two-liquid mixing microreactor 110A to perform a temperaturecontrol of a reaction solution. The silver nitrate solution and the KBrsolution were added to the microreactor by syringe pumps. TABLE 1Variation coefficient Average Tubular Circle equivalent (%) of circlethickness grain ratio Emulsion diameter (Mm) equivalent diameter (μm)(%) Content 1-A 1.3 21 0.045 98 Comparative example 2-A 1.4 16 0.045 99Example

[0456] As shown in Table 1, it is understood that the size distributionof the tabular grains is narrow in this example.

[0457] 2.4×10⁻⁴ mol/mol Ag of the following compound was added to theemulsions 1-A and 1-B at 40° C. prepared as described above, and sodiumthiosulfate, potassium gold chloride, and potassium thiocyanate wereadded thereto, and subjected to optimum chemical sensitization at 60° C.

[0458] (1) Emulsion layer

[0459] Emulsion . . . various kinds of emulsions (silver 3.6×10⁻² mo/m²)Coupler (1.5×10⁻³ mol/m²) described below.

[0460] (Compound)

[0461] (Compound)

[0462] tricresyl phosphate (1.10 g/m²)

[0463] gelatin (2.30 g/m²)

[0464] (2) Protective Layer

[0465] 2,4-dichloro-6-hydroxy-S-triazine Sodium Salt (0.08 g/m²) Gelatin(1.80 g/m²)

[0466] After these samples were allowed to stand at 40° C. and relativehumidity of 70% for 14 hours, the samples were exposed through a yellowfilter and a continuous wedge for {fraction (1/100)} second, and werecolor-processed according to the following process. [Color development]processing Process processing time temperature Color development 2minutes 00 second 40° C. Breach-fixation 3 minutes 00 second 40° C.Washing (1) 20 seconds 35° C. Washing (2) 20 second 35° C. Stabilization20 seconds 35° C. Drying 50 seconds 65° C.

[0467] Hereinafter, the compositions of processing solutions aredescribed. (Unit: g) (Color development) diethylenetriamine pentaaceticacid 2.0 1-hydroxyethylidene-1,1-disulphone 4.0 sodium sulfite potassiumcarbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mghydroxylamine sulfate 2.4 4-[N-ethyl-N-β-hydroxyethylamino]- 4.52-methylaniline sulfate water up to 1.0 liter pH 10.05 (Bleach-fixingsolution) ethylenediaminetetraacetic acid 90.0 ferric ammonium dihydratedisodium ethylenediaminetetraacetate 5.0 sodium sulfite 12.0 ammoniumthiosulfate solution (70%) 260.0 ml acetic acid (98%) 5.0 ml

water up to 1.0 liter pH 6.0

[0468] (Washing Solution)

[0469] Tap water was made to flow through a mixed bed column filled withH form cation exchange resin (Amberlite IR-120B made by Rohm and HaasCompany) and OH form anion exchange resin (Amberlite IR-400 made by Rohmand Haas Company), the concentration of calcium and magnesium ions wasprocessed to 3 mg/liter or less, and subsequently, 20 mg/liter of sodiumdichloro isocyanurate and 1.5 g/liter of sodium sulfate were added.

[0470] The pH value of this liquid is within the range of 6.5 to 7.5.(Stabilizing solution) (Unit: mg) formalin (37%) 2.0 mlpolyoxyethylene-p-monononylphenyl ether 0.3 (average polymerizationdegree 10) disodium ethylenediaminetetraacetate 0.05 water up to 1.0liter pH 5.0 to 8.0

[0471] The results are shown in Table 2. The sensibility was expressedby relative values of a logarithm of an inverse number to lightexposure, which gives density of 0.1 above fogging value and isexpressed by lux second. TABLE 2 Emulsion Sensitivity Fogging GradationContent 1-A 100 0.06 1.7 Comparative example 2-A 104 0.06 1.9 Example

[0472] As shown in Table 2, the emulsion of the invention has a highgradation. This is a result from the fact that the size distribution ofthe tabular grains becomes narrow by the invention, so that thegradation becomes high.

[0473] In addition, in the foregoing example, the silver halidephotographic emulsion of the high quality reaction product containingthe tabular grains having a high aspect ratio and a narrow grain sizedistribution was obtained.

Example of a Microreactor

[0474] Next, microreactor devices that can be used in each embodiment ofthe invention will be described with reference to FIGS. 20 and 21.

[0475] The microreactor device is constituted as a mixing microreactordevice 122 having amixing structure, for example, illustrated in FIG.20. In this mixing microreactor device 122, a channel member 126 isintegrally disposed so as to cross a flow passage 124 formed into aminute rectangular groove shape.

[0476] This channel member 126 is formed into a corrugated partitionplate which crosses and divides the flow passage 124, and constructsplural microchannels formed to be U-shaped.

[0477] A cover member 128 is fixed to an upper surface of the flowpassage 124 shown in FIG. 20, and a minute rectangular shape is formedas a whole. A slit-shaped outlet 130 is bored in the cover member 128 ata predetermined position corresponding to the channel member 126. Theoutlet 130 is constituted to be connected to an unillustrated deliveryport of a process liquid, and to deliver a mixed process liquid.

[0478] The mixing microreactor 122 constituted as stated above is such adevice that two fluids flowing from both sides of the flow passage 124shown in FIG. 20 enter the respective U-shaped channels of the channelmember 126 to substantially form thin layers, and when the two fluidsentering the adjacent U-shaped channels flow into the slit-shaped outlet130, an open interface is formed between the adjacent two fluids, thethickness of each of the thin layers of these two fluids becomes amicrometer size in the normal direction of the contact interface, andmovement like mutual diffusion from the open interface between thefluids occurs to produce a reaction and the like, so that a chemicalchange continuously occurs.

[0479] Since the mixing microreactor device 122 brings about a chemicalchange while the flow of laminar flow takes place in one direction, achemical reaction does not occur at a place where the so-called localrecycling occurs in which circulating flow occurs.

[0480] In addition, as a microreactor device provided with a mixingfunction, a heat exchange function, and a straightening function, forexample, a multi function microreactor device 132 exemplified in FIG. 21has been known.

[0481] This multi function microreactor device 132 is constituted as onemodule in such a way that two delay plates 136 provided with a structurefor supplying a supply fluid after straightening or delaying the fluidare superposed to the lower part of an upper plate 134, a liquid supplyplate 138 is disposed under the lower plate 136, a reaction plate 140 isdisposed under the supply plate 138 to mix two liquids and allow toreact the liquids with each other and further to perform a temperaturecontrol by making a heat exchange with the reaction solution, and abottom plate 142 is disposed under the plate 140. These plates areintegrally fastened together to form the module.

[0482] In the multi function microreactor device 132, two kinds ofprocess liquids are introduced from unillustrated introduction ports forprocess liquids provided in the upper plate 134 or the bottom plate 142,and after straightening is performed by the delay plate 136, the liquidsare fed through the liquid supply plate 138 to the reaction plate 140,where the two kinds of process liquids are subjected to the temperaturecontrol and are mixed to react with each other, and a reacted processliquid is delivered from an unillustrated discharge port provided in theupper plate 134 or the bottom plate 142.

[0483] Next, an eighth embodiment concerning a production apparatuswhich can be used for a production method of silver halide photographicemulsion of the invention will be described with reference to FIGS. 22to 29.

[0484] The eighth embodiment has an object to provide a microreactorwhich can easily form, in a mixer body, fluid supply passages, thenumber of which is equal to the number of kinds of fluids to be mixedeven in the case where there are three or more kinds of fluids to bemixed, and can supply these fluids from these fluid supply passages tomixing flow passages in the form of lamella-like laminar flows,respectively.

[0485] To this end, in the micromixer (microreactor) of this embodiment,a first fluid supply passage formed along the surface part of a baseplate is provided with a first header part which is bored in the surfacepart of the base plate and to which a fluid is supplied from the outsideof a mixer body, and a slit-shaped first supply port which is connectedwith the first header part and is bored in the surface part of the baseplate, and a second fluid supply passage formed in the base plate isprovided with a second header part which is bored in a back surface partof the base plate and to which a fluid is supplied from the outside ofthe mixer body, and a slit-shaped second supply port which is connectedwith the second header part through a through part passing through thebase plate, and is bored in the surface part of the base plate so as tobe adjacent to the first supply port in the width direction, whereby itbecomes unnecessary to form the header part in the second fluid supplypassage and a minute groove part (microchannel part) for connecting theheader part to the second supply port in the front surface part of thebase plate.

[0486] Accordingly, even in the case where at most two first fluidsupply passage can only be formed in the front surface part of the baseplate by restriction in space, the second supply port having a minuteopening width of 1 μm to 50 μm is bored in the front surface part of thebase plate, so that the fluid can be introduced to the mixing flowpassage formed in the mixing plate through the first supply port and thesecond supply port, and accordingly, if one or two second fluid supplypassages are formed in the base plate, two kinds to four kinds of fluidsare introduced to the mixing flow passage through the first and thesecond fluid supply passages, and while these fluids are made laminarflows having minute widths corresponding to the open widths of the firstand the second supply ports and are made to flow in the mixing flowpassage, these fluids can be diffused and mixed.

[0487] Furthermore, according to the micromixer of the invention,especially in the case where the supply port in the fluid supply passagebranches into plural parts from the header part and is arranged like theteeth of a comb, the plural supply ports connected to the differentfluid supply passages are alternately disposed, and the maximum numberof fluid supply passages formed in one side surface (front surface partor back surface part) of the base plate are actually limited to two.However, even in such a case, the microreactor that can mix three orfour kinds of fluids can be easily realized.

[0488] Moreover, in the micromixer of the invention, as fluids suppliedto the plural flow supply passages from the outside, for example, aliquid, a gas, a solid liquid mixture in which metal fine particles orthe like are dispersed in liquid, a solid gas mixture in which metalfine particles or the like are dispersed in gas, a gas liquid mixture inwhich gas is dispersed in liquid without being dissolved are alsoobjects. That the kind of fluid is different includes not only a casewhere chemical compositions are different, but also a case where a stateof temperature, solid liquid ratio or the like is different.

[0489] (No. 1 of Eighth Embodiment)

[0490]FIGS. 22 and 23 show an example of a micromixer according to No. 1of the eighth embodiment of the invention. This micromixer 1010 mixesthree kinds of solutions L1, L2 and L3 simultaneously, and produces asolution LM in which these solutions L1, L2 and L3 are uniformly mixed.Here, when the solutions L1, L2 and L3 are mixed by a micromixer 1010,it is conceivable that a chemical reaction occurs between the solutionsL1, L2 and L3 in some case and a chemical reaction does not occur inanother case, and the micromixer of this embodiment can be used for boththe cases.

[0491] As shown in FIG. 22, the micromixer 1010 is formed to besubstantially cylindrical as a whole, and a base plate 1012, a mixingplate 1014, and cover plates 1016 and 1018 are stacked in the thicknessdirection (direction of an arrow T) of the plate. These four plates1012, 1014, 1016 and 1018 are respectively formed to have disk shapeshaving the same outer diameter. Here, the base plate 1012 and the mixingplate 1014 constitute a mixer body 1020 for mixing the solutions L1, L2and L3, and the cover plates 1016 and 1018 are disposed so that themixer body 1020 is sandwiched between plates 1016 and 1018 in thethickness direction. Incidentally, on the paper surface of FIG. 22B, asurface positioned at the upper side of each of the plates 1012, 1014,1016 and 1018 is referred to as a front surface part, and a surfacepositioned at the lower side of each of the plates 1012, 1014, 1016 and1018 is referred to as a back surface part.

[0492] Plural insertion holes 1022, 1024, and 1026 passing through inthe thickness direction are bored in the cover plate 1016, the mixingplate 1014, and the base plate 1012 at the outer peripheral parts.Plural screw holes 1028 corresponding to the plural insertion holes1022, 1024 and 1026 are bored in the outer peripheral part of the coverplate 1018 in the thickness direction. After the plates 1012, 1014, 1016and 1018 are superposed so that the insertion holes 1022, 1024 and 1026and the screw holes 1028 coincide with each other, coupling bolts 1030are inserted from the side of the cover plate 1016 into the insertionholes 1022, 1024 and 1026, and are screwed into the screw holes 1028 ofthe cover plate 1018, so that the plates are coupled by the couplingbolts 1030 and are assembled as the micromixer 1010.

[0493] As shown in FIG. 22B, a circular groove 1032 is formed in each ofa back surface part 1016B of the cover plate 1016, a back surface part1014B of the mixing plate 1014, and a front surface part 1018A of thecover plate 1018 in the peripheral direction at a slightly innerperipheral side with respect to the insertion hole 1024 or 1026 or thescrew holes 1028, and an O-ring 1034 (see FIG. 23) made of elasticmaterial such as silicone rubber is inserted in each of these circulargrooves 1032. These three O-rings 1034 are respectively compressed inthe thickness direction between the plates 1014 and 1016, between theplates 1012 and 1014, and between the plates 1012 and 1018, and preventthe leak of the solutions L1, L2, L3 and LM from the interfaces of theplates 1012 and 1014, the plates 1014 and 1016, and the plates 1012 and1018.

[0494] As shown in FIG. 23, a recess-shaped liquid supply passage 1036is formed in the front surface part 1012A of the base plate 1012. In theliquid supply passage 1036, a header part 1038 is provided at a portionnear the outer periphery of the front surface part 1012, and the shapeof this header part 1038 in the surface direction is a fan shape inwhich its width widens from the outer peripheral side to the centerside. In the liquid supply passage 1036, plural (six in FIG. 23)microchannel parts 1040 extending from the center end part of the headerpart 1038 are integrally formed. These microchannel parts 1040 arerespectively formed to have thin and long groove shapes extending inparallel with each other in the diameter direction of the base plate1012, and are arranged like the teeth of a comb as a whole. In each ofthe plural microchannel parts 1040, a slit-like liquid supply port 1042is bored in the front surface part 1012A of the base plate 1012, and anopening width W1 (see FIG. 23) of the liquid supply port 1042 issuitably set within the range of from 1 μm to 500 μm in accordance withthe kind, supply amount and the like of the solution L1. Further, thedepth of the microchannel part 1040 is also suitably set in accordancewith the supply amount of the solution L1, and is preferably set to beone or more times as long as the opening width W1, and is morepreferably set to be two or more times as long as the opening width W1.The number of the microchannel parts 1040 extending from the header part1038 is also suitably set in accordance with the supply amount of thesolution L1, and in the case where the opening width W1 is constant, itis necessary to increase the number in accordance with the increase ofthe supply amount.

[0495] As shown in FIGS. 24D and 25, a pair of recess-shaped liquidsupply passages 1044 and 1054 are formed in the back surface part 1012Bof the base plate 1012. Also in these liquid supply passages 1044 and1054, header parts 1046 and 1056 having the same shape as the liquidsupply passage 1036 in the front surface part 1012A are formed, andthese header parts 1046 and 1056 are symmetrically arranged with respectto the axial center S of the micromixer 1010. In the one liquid supplypassage 1044, plural (six in FIGS. 25 and 25) microchannel parts 1048are integrally formed from the center end part of the header part 1046.These microchannel parts 1048 are respectively formed to have thin andlong groove shapes extending in parallel with each other in the diameterdirection, and are disposed like the teeth of a comb as a whole. Thesemicrochannel parts 1048 deviate respectively from the microchannel parts1040 of the liquid supply passage 1036 by a predetermined distance inthe channel width direction (direction of an arrow W), and are disposedto substantially coincide with the microchannel parts 1040 in thechannel length direction (direction of an arrow E).

[0496] Also in the other liquid supply passage 1054, plural (six inFIGS. 24 and 25) microchannel parts 1058 are integrally formed from thecenter end part of the header part 1056. These microchannel parts 1058are respectively formed to have thin and long groove shapes extending inparallel with each other in the diameter direction, and are disposedlike the teeth of a comb as a whole. These microchannel parts 1058 arerespectively positioned between the microchannel parts 1040 and themicrochannel parts 1048 in the channel width direction, and are disposedto substantially coincide with the microchannel parts 1048 and 1058 inthe channel length direction. Here, the back surface part 1014B of themixing plate 1014 comes in close contact with the front surface part1012A of the base plate 1012, so that the opening of the liquid supplypassage 1036 at the side of the mixing plate 1014 is closed by this backsurface part 1014B, and a space divided from the outside is formed inthe liquid supply passage 1036. The front surface part 1018A of thecover plate 1018A comes in close contact with the back surface part1012B of the base plate 1012, so that the openings of the liquid supplypassages 1044 and 1054 at the side of the cover plate 1018 are closed bythis front surface part 1018A, and spaces divided from the outside arerespectively formed in the liquid supply passages 1044 and 1054.

[0497] As shown in FIGS. 24B and 24C, through parts 1050 and 1060 areformed in the liquid supply passages 1044 and 1054 to pass through fromthe bottom portions of the microchannel parts 1048 and 1058 to the frontsurface part 1012A of the base plate 1012 in the thickness direction.The opening ends of these through parts 1050 and 1060 at the frontsurface part 1012A are made thin and long slit-like liquid supply ports1052 and 1062 in the channel length direction. As shown in FIG. 24A,these liquid supply ports 1052 and 1062 extend in parallel with theliquid supply port 1042 of the liquid supply passage 1036. The threekinds of liquid supply ports 1042, 1052 and 1062 are disposedalternately in the channel width direction. Here, similarly to theliquid supply port 1042, the opening widths W2 and W3 of the liquidsupply ports 1052 and 1062 in the channel width direction are suitablyset within the range of from 1 μm to 500 μm in accordance with the kind,supply amount and the like of the solutions L2 and L3, and the openingwidths W1, W2 and W3 in this embodiment are made to have the same size.It is preferable that the pitch among the three kinds of liquid supplyports 1042, 1052 and 1062 in the channel width direction is as narrow aspossible from the viewpoint of the suppression of the occurrence ofstagnation and the shortening of the mixing time of the solutions L1, L2and L3.

[0498] As shown in FIGS. 23 and 26, a mixing flow passage 1064 piercingfrom the back surface part 1014B to the front surface part 1014A isbored in the center of the mixing plate 1014. The cross-sectional shapeof this mixing flow passage 1064 is made a slit shape which is thin andlong in the direction (channel width direction) orthogonal to the liquidsupply ports 1042, 1052 and 1062 and the opening width of which isnarrow in the channel length direction. The opening length of the mixingflow passage 1064 in the channel width direction becomes narrow like ataper from the back surface part 1014B to the front surface part 1014A,and a liquid incoming port 1066 and a liquid outgoing port 1068 thin andlong in the channel width direction are respectively bored in the backsurface part 1014B and the front surface part 1014A. The liquid incomingport 1066 faces the liquid supply ports 1042, 1052 and 1062 of the baseplate 1012, and is disposed to cross the center part of the liquidsupply ports 1042, 1052 and 1062 in the channel width direction.Accordingly, the liquid supply passages 1036, 1044 and 1054 are in thestate where only the centers of the liquid supply ports 1042, 1052 and1062 communicate with the mixing flow passage 1064 through the liquidincoming port 1066. Here, the opening width W4 (see FIG. 23) of themixing flow passage 1064 in the channel length direction is suitably setwithin the range of from 1 μm to 500 μm in accordance with the openingwidths W1, W2 and W3 of the liquid supply ports 1042, 1052 and 1062 andthe liquid supply quantities of the solutions L1, L2 and L3 from theliquid supply ports 1042, 1052 and 1062.

[0499] As shown in FIG. 22, two liquid injection holes 1070 and 1072 arebored in the lower cover plate 1018 in the thickness direction, andthese liquid injection holes 1070 and 1072 pass through the cover plate1018. End parts of the liquid injection holes 1070 and 1072 arerespectively connected to the header parts 1046 and 1056 in the liquidsupply passages 1044 and 1054, and female screw parts 1070A and 1072Aare respectively formed at the other end parts. Male screw parts ofnipple members 1074 formed into tubes are screwed in these female screwparts 1070A and 1072A. Liquid supply pipes (not shown) are connected tothe pair of liquid injection holes 1070 and 1072 through the pair ofnipple members 1074, and the pressurized solutions L2 and L3 aresupplied through the pair of liquid supply pipes.

[0500] Also in the mixing plate 1014 and the upper cover plate 1016,liquid injection holes 1076 and 1078 are bored in the thicknessdirection, these liquid injection holes 1076 and 1078 respectively passthrough the mixing plate 1014 and the cover plate 1016, and areconnected to each other at the interface between the mixing plate 1014and the back surface part 106B of the cover plate 1016. One end part ofthe liquid injection hole 1076 is connected to the header part 1038 inthe liquid supply passage 1036, and a female screw part 1078A is formedat the other end part of the liquid injection passage 1078. The malescrew part of the nipple member 1074 is screwed in this female screwpart 1078A. Liquid supply pipes (not shown) are connected to the liquidinjection holes 1076 and 1078 through the nipple members 1074, and thepressurized solution L1 is supplied through this liquid supply pipe. Inaddition, a circular groove is formed in the back surface part 1016B ofthe cover plate 1016 at the outer peripheral side of the liquid supplypassage 1078, an O-ring 1019 is inserted in this circular groove asshown in FIG. 1B, and this O-ring is compressed between the cover plate1016 and the mixing plate 1014 in the axial direction. This prevents thesolution L3 flowing in the liquid injection holes 1076 and 1078 fromleaking out from a portion between the back surface part 1016B of thecover plate 1016 and the front surface part 1014A of the mixing plate1014.

[0501] As shown in FIG. 22, a liquid outgoing port 1080 is bored in theupper cover plate 1016 along the axial center S, and this liquidoutgoing port 1080 pierces the cover plate 1016. One end part of theliquid outgoing hole 1080 is connected to the liquid outgoing port 1068of the mixing flow passage 1064, and a female screw part 1080A is formedat the other end part. A male screw part of a nipple member 1082 formedinto a tube is screwed in this female screw part 1080A. A liquidoutgoing pipe (not shown) is connected to the liquid outgoing hole 1080through the nipple member 1082. By this, the solution LM in which thethree kinds of solutions L1, L2 and L3 are mixed is supplied to theliquid outgoing pipe through the liquid outgoing hole 1080, and is sentthrough this liquid outgoing pipe to another micromixer in which a nextprocess is performed or a solution tank for storing the solution LM.

[0502] In the micromixer 1010 of the embodiment constituted as describedabove, the solutions L1 to L3 are supplied to the header parts 1038,1046 and 1056 formed in the front surface part 1012A and the backsurface part 1012B of the base plate 1012 through the liquid injectionholes 1070, 1072, 1076 and 1078, so that these solutions L1 to L3 areintroduced into the mixing flow passage 1064 through the liquid supplyport 1042, 1052 and 1062 of the microchannel parts 1040, 1048 and 1058.At this time, since the opening widths W1 to W3 of the liquid supplyports 1042, 1052 ad 1062 are made very small widths of 1 μm to 500 μm,the solutions L1 to L3 discharged from the liquid supply ports 1042,1052 and 1062 into the mixing flow passage 1064 respectively becomelamellar-shaped laminar flows having widths corresponding to the openingwidths W1 to W3, and flow from the liquid incoming port 1066 to the sideof the liquid outgoing port 1068, molecular diffusion occurs at theinterface of the respective laminar flows in the normal direction, andthe solutions L1 to L3 are mixed, so that the solution LM in which thesolutions L1 to L3 are uniformly mixed is generated at the front side ofthe liquid outgoing port 1068. Accordingly, according to the micromixer1010, the three kinds of solutions L1 to L3 are simultaneously mixed inthe mixing flow passage 1064, and after the solutions are uniformlymixed, or a required chemical reaction, together with the mixing, iscompleted, the obtained solution LM can be supplied to the liquidoutgoing pipe connected to the nipple member 1082.

[0503] Next, a modified example of the micromixer of the eighthembodiment of the invention will be described. FIGS. 27 and 28respectively show modified examples of the micromixer of the eighthembodiment of the invention.

[0504] A micromixer 1086 shown in FIG. 27, similar to the micromixer1010 as shown in FIGS. 22 and 23, is for generating the solution LM bymixing three kinds of solutions L1, L2 and L3. Main changing points ofthe micromixer 1086 with respect to the micromixer 1010 are that the oneliquid supply passage 1054 formed in the back surface part 1012B of thebase plate 1012 is omitted, and a liquid supply passage 1088 is addedand formed in the front surface part 1012A of the base plate 1012.

[0505] The liquid supply passage 1088 added to and formed in the frontsurface part 1012A of the base plate 1012, similar to the other liquidsupply passage 1036, is provided with a header part 1090 and amicrochannel part 1092, and is disposed symmetrically with the otherliquid supply passage 1036 with respect to the axial center S. In themicromixer 1086, correspondingly to these main changing points, oneliquid injection hole 1072 passing through the lower cover plate 1018 isomitted, and liquid injection holes 1096 and 1098 are added and bored inthe mixing plate 1014 and the upper cover plate 1016. The liquidinjection holes 1096 and 1098 are made to have similar shapes to theother liquid injection holes 1076 and 1078, the one end part isconnected to the header part 1090 of the liquid supply part 1088 addedand formed in the front surface part 1012A, and a female screw part (notshown) is formed at the other tip end. The nipple member 1074 (see FIG.22), similar to the other liquid injection holes 1076 and 1078, isscrewed in this female screw part. Liquid supply pipes (not shown) areconnected to the liquid injection holes 1096 and 1098 through the nipplemember 1074, and the pressurized solution L3 is supplied through thisliquid supply pipe.

[0506] As shown in FIG. 27A, the microchannel part 1040 of the liquidsupply passage 1036 formed in the front surface part 1012A of the baseplate 1012 and the microchannel part 1092 of the liquid supply passage1088 are disposed to be adjacent to each other in the channel widthdirection, and the liquid supply port 1042 and the liquid supply port1094 are bored in the front surface part 1012A. Here, an opening widthW5 of the liquid supply port 1094 in the channel width direction,similar to the other liquid supply port 1042, is suitably set within therange of from 1 μm to 500 μm in accordance with the kind, supply amountand the like of the solution L3. The depth of the microchannel part1092, similar to the other microchannel part 1040,is also set to bepreferably 1 or more times as long as the opening width W1, morepreferably 2 or more times as long as the opening width W4. These liquidsupply ports 1042 and 1094 and the liquid supply port 1052 connected tothe liquid supply passage 1044 formed in the back surface part 1012B arealternately disposed in the channel width direction. These liquid supplyports 1042, 1052 and 1094 are respectively connected to the liquidincoming port 1066 of the mixing flow passage 1064. By this, thesolutions L1, L2 and L3 are introduced through the liquid supply ports1042, 1052 and 1094 and the liquid incoming port 1066 from the liquidsupply passages 1036, 1044 and 1088 into the mixing flow passage 1064,and are supplied, as the solution LM, through this mixing flow passage1064 to the liquid outgoing pipe.

[0507] Also by the micromixer 1086 of this embodiment constituted asdescribed above, similarly to the micromixer 1010 shown in FIGS. 22 and23, the three kinds of solutions L1 to L3 are simultaneously mixed inthe mixing flow passage 1064, and after these solutions are uniformlymixed or a required chemical reaction, together with the mixing, iscompleted, the obtained solution LM can be supplied to the liquidoutgoing pipe connected to the nipple member 1082.

[0508] A micromixer 1100 as shown in FIG. 28 is for mixing four kinds ofsolutions L1, L2, L3 and L4 to form a solution LM. A main changing pointof this micromixer 1100 with respect to the micromixer 1010 is that aliquid supply passage 1102 is additionally formed in a front surfacepart 1012A of a base plate 1012.

[0509] The liquid supply passage 1102 formed in the front surface part1012A of the base plate 1012, similar to the other liquid supply passage1036, is provided with a header part 1104 and a microchannel part 1106,and is disposed symmetrically with the other liquid supply passage 1036with respect to the axial center S. In the micromixer 1100,corresponding to this main changing point, liquid injection holes 1096and 1098 communicating with each other are additionally bored in themixing plate 1014 and the upper cover plate 1016. The liquid injectionholes 1096 and 1098 are made to have the same shape as the other liquidinjection holes 1076 and 1078, and the one end part is connected to theheader part 1104 of the liquid supply passage 1102 additionally formedin the front surface part 1012A. A female screw part (not shown) isformed in the other end part of the liquid injection hole 1098, and thenipple member 1074 (see FIG. 22) is screwed in this female screw part.Liquid supply pipes (not shown) are connected to the liquid injectionholes 1096 and 1098 through the nipple member 1074, and the pressurizedsolution L4 is supplied through this liquid supply pipe.

[0510] As shown in FIG. 28A, the microchannel part 1040 of the liquidsupply passage 1036 formed in the front surface part 1012A of the baseplate 1012 and the microchannel part 1106 of the liquid supply passage1102 are disposed to adjacent with each other, while the liquid supplyport 1052 or the liquid supply port 1062 intervenes therebetween in thechannel width direction, and the liquid supply port 1042 and the liquidsupply port 1094 are bored in the front surface part 1012A. Here,similarly to the other liquid supply ports 1042, 1052 and 1062, anopening width W6 of the liquid supply port 1094 in the channel widthdirection is suitably set within the range of from 1 μm to 500 μm inaccordance with the kind, supply amount and the like of the solution L4.These liquid supply ports 1042, 1052, 1062 and 1098 are disposedalternately in the channel width direction. These four kinds of liquidsupply ports 1042, 1052, 1062 and 1094 are respectively connected to theliquid incoming port 1066 of the mixing flow passage 1064. By this, thesolutions L1, L2, L3 and L4 supplied into the liquid supply passages1036, 1044, 1054 and 1102 through the liquid supply pipe are introducedinto the mixing flow passage 1064 through the liquid supply ports 1042,1052, 1062 and 1094 and the liquid incoming port 1066, and are suppliedas the solution LM to the liquid outgoing pipe through the mixing flowpassage 1064.

[0511] According to the micromixer 1100 of the embodiment constituted asdescribed above, four kinds of solutions L1 to L4 are simultaneouslymixed in the mixing flow passage 1064, and after these solutions areuniformly mixed or a required chemical reaction, together with themixing, is completed, the obtained solution LM can be supplied to theliquid outgoing pipe connected to the nipple member 1082.

[0512] Next, a production method of the micromixers 1010, 1086 and 1100of this embodiment will be described. With respect to the raw materialof each of the plates 1012, 1014, 1016 and 1018 constituting themicromixers 1010, 1086 and 1100, it is necessary to consider strength,chemical stability such as corrosion resistance to the solutions L1 toL4, fluidity at the contact interface to the solutions L1 to L4, and thelike, and specifically, for example, stainless (SUS system), nonferrousmetals, fine ceramics, special ceramics, plastic or the like is used,and what is obtained by applying a surface treatment, such as coating,to the material as the need arises, is used as the material of theplates 1012, 1014, 1016 and 1018. These materials and main processingmethods for processing these materials are shown in Table 3 describedbelow. TABLE 3 Main processing Example of material method (1) MetalMetal material such as SUS, Ni, Ultra-fine machining, material Al, Cu,Ag, Au, Pt, Ta or Ti, alloy electric discharge material such as Ni—Fe orAu—Pt machining, dry etching such as ICP (2) Fine Glass, Al₂O₃Ultra-fine machining, ceramics electric discharge machining, dry etchingsuch as ICP (3) Special Machinable ceramic, conductive Ultra-finemachining, ceramics ceramic such as SiC, etc. electric dischargemachining, dry etching such as ICP (4) Plastic Acrylic resin, etc.Ultra-fine machining (5) Ceramic TiN, SiC MOCVD, plasma coating layerCVD

[0513] For example, in the case where the base plate 1012 is formed ofmetal material, the liquid supply passage 1036 can be processed in thisbase plate 1012 by a method as described in the following paragraphs (1)to (3).

[0514] (1) After the microchannel part 1040 is carved and formed in thefront surface part 1012A of the base plate 1012 by the electricaldischarge machining, the front surface part 1012A is subjected to diecutting electrical discharge machining by using an electrode having asurface shape corresponding to an opening shape of the header part 1038,and the header part 1038 is formed.

[0515] (2) After the header part 1038 is formed in the front surfacepart 1012A of the base plate 1012 by die cutting electrical dischargemachining, the microchannel part 1040 is formed by electrical dischargemachining using a minute electrode having a diameter of several μm toapproximately 20 μm corresponding to the opening width W1.

[0516] (3) In the case where the opening width W1 of the microchannelpart 1040 is wider than approximately 10 μm, the microchannel part 1040is formed in the front surface part 1012A of the base plate 1012 by fineelectrical discharge machining using an electrode corresponding to agroove shape of the microchannel part 1040, or after the microchannelpart 1040 is formed by using ultra-fine machining (micro cuttingmachining), the header part 1038 is formed by die cutting electricaldischarge machining.

[0517] In the case where the liquid supply passages 1044 and 1054 areformed in the base plate 1012, after the microchannel parts 1048 and1058 and the header parts 1046 and 1057 are formed in the back surfacepart 1012B of the base plate 1012 by some method described in the aboveparagraphs (1) to (3), the through holes 1050 and 1060 passing throughfrom the bottom portions of the microchannel parts 1048 and 1058 to thefront surface part 1012A are formed by electrical discharge workingusing a minute electrode, so that these liquid supply passages 1044 and1054 can also be formed.

[0518] In the case where the base plate 1012 is formed of material withno electoconductivity, such as glass, the liquid supply passages 1036,1044, 1054, 1088 and 1100 can be formed in the base plate 1012 by, forexample, ultra-fine cutting machining, or dry etching machining such asICP.

[0519] Further, in the micromixers 1010, 1086 and 1100, as an equivalentdiameter (an inner diameter in the case where the sectional shape of achannel is converted into a circle) of each of the microchannel parts1040, 1048, 1058, 1092 and 1106 becomes small, there is a fear that theinfluence of viscosity of the solutions L1 to L4 is increased, and thefluidity is deteriorated. Such decrease in the fluidity can beeffectively prevented by, for example, finishing the inner surfaces ofthe microchannel parts 1040, 1048, 1058, 1092 and 1106 into ultra-smoothsurfaces of R_(max)≦0.2 μm by wet polishing using an agent such as anacid solution, or in contrast with this, by performing a surfaceroughening treatment such as a stain crape treatment. Furthermore, it isalso effective to apply ceramic coating of Si₃N₄, SiO₂ or Al₂O₃ to theinner surfaces of the microchannel parts 1040, 1048, 1058, 1092 and 1106for the purpose of preventing the decrease in the fluidity. As amaterial effective in preventing the decrease in the fluidity, forexample, SUS 316 can be named.

[0520] When it is expected that especially the solutions L1 to L4 havinghigh corrosiveness is processed, the corrosion resistance to thesolutions L1 to L4 having corrosiveness can be improved by applyingcoating of TEFLON™, TiN or SiC to the contact parts of the respectiveplates 1012, 1014, 1016 and 1018 with respect to the solutions L1 to L4,or by plating these parts with metal, such as gold (Au), having a highchemical stability.

[0521] (No. 2 of the Embodiment of FIG. 8)

[0522]FIG. 29 shows a micromixer according to No.2 of the eighthembodiment of the invention. A solution LM is formed by mixing eightkinds of solutions L1 to L8 by using the micromixer 1110. Incidentally,in the micromixer 1110 as shown in FIG. 29, members common to themicromixers 1010, 1086 and 1100 of the eighth embodiment in thestructure and operation are designated by the same symbols and thedescriptions are omitted.

[0523] In the micromixer 1110 of this embodiment, as shown in FIG. 29B,a mixer body 1112 is constituted such that two base plates 1114 and 1116are superposed through a seal plate 1122, and further, one mixing plate1014 is superposed on the base plate 1116. The micromixer 1110 isassembled such that cover plates 1016 and 1018 are superposed on bothsides of the mixer body 1112, respectively, and these are coupled by acoupling bolt (not shown). In the base plate 1114 as shown in the lowerside of FIG. 29B, a pair of liquid supply passages 1118 and 1124 areformed in its front surface part 1114A, and a pair of liquid supplypassages 1130 and 1136 are formed in its back surface part 1114B. Alsoin the upper base plate 1116, similar to the lower base plate 1114, apair of liquid supply passages 1148 and 1154 are formed in its frontsurface part 1116A, and a pair of liquid supply passages 1160 and 1166are formed in its back surface part 1116B.

[0524] The liquid supply passages 1118 and 1124 and the liquid supplypassages 1130 and 1136 formed in the lower base plate 1114 havebasically the same structure as the liquid supply passages 1044 and 1054and the liquid supply passages 1036 and 1102 formed in the base plate1012 of the micromixer 1100 of the eighth embodiment, and respectivelyinclude header parts 1119, 1125, 1131 and 1137, plural (two in thisembodiment) microchannel parts 1120, 1126, 1132 and 1138 extending frominner peripheral side end parts of these header parts 1119, 1125, 1131and 1137, and through parts 1133 and 1139 passing through from thebottom portions of the microchannel parts 1132 and 1138 to the frontsurface part 1114A.

[0525] Here, four liquid injection holes 1142, 1143, 1144 and 1145, endparts of which are connected to the header parts 1119, 1125, 1131 and1137 and the other end parts of which are opened to the outside of themicromixer 1110, are bored in the lower cover plate 1018 and the baseplate 1114. Liquid supply pipes (not shown) are connected to the otherend parts of these liquid injection holes 1142, 1143, 1144 and 1145, andthe solutions L1 to L4 are supplied to the header parts 1119, 1125, 1131and 1137 through these liquid supply pipes and the liquid injectionholes 1142, 1143, 1144 and 1145.

[0526] The liquid supply passages 1148 and 1154 and the liquid supplypassages 1160 and 1166 formed in the upper base plate 1116 also have thesame structure as the liquid supply passages 1044 and 1054 and theliquid supply passages 1036 and 1102 formed in the base plate 1012 ofthe micromixer 1100 of the eighth embodiment, and respectively includeheader parts 1149, 1155, 1161 and 1167, plural (two in this embodiment)microchannel parts 1150, 1156, 1162 and 1168 extending from the innerperipheral side end parts of these header parts 1149, 1155, 1161 and1167, and through parts 1163 and 1169 (see FIG. 29B) piecing from thebottom portions of the microchannel parts 1162 and 1168 to the frontsurface part 1116A.

[0527] Here, four liquid injection holes (not shown), end parts of whichare connected to the header parts 1149, 1155, 1161 and 1167 and theother end parts of which are opened to the outside of the micromixer1110, are bored in the upper cover plate 1016, the mixing plate 1014 andthe upper base plate 1116. Liquid supply pipes (not shown) are connectedto the other end parts of these liquid injection holes 1172, 1173, 1174and 1175, and the solutions L5 to L8 are respectively supplied to theheader parts 1149, 1155, 1161 and 1167 through these liquid supply pipesand the liquid injection holes 1172, 1173, 1174 and 1175.

[0528] As shown in FIG. 29B, extension passages 1178, 1180, 1182 and1184 passing through from the back surface part 1116B to the frontsurface part 1116A are bored in the upper base plate 1116. Here, in theextension passages 1178 and 1180, lower open ends are connected to thethrough parts 1133 and 1139 bored in the front surface part 1114A of thebase plate 1114, and upper open ends are bored in the front surface part1116A of the base plate 1116 to form liquid supply ports 1179 and 1181.In the extension passages 1182 and 1184, lower open ends are connectedto the microchannel parts 1120 and 1126 bored in the front surface part1114A of the base plate 1114, and upper open ends are bored in the frontsurface part 1116A of the base plate 1116 to form liquid supply ports1183 and 1185. In the seal plate 1122, the through parts 1133 and 1139and opening parts piercing in the thickness direction at the portionsopposite to the microchannel parts 1120 and 1126 are formed, and theseopening parts respectively constitute parts of the extension passages1178, 1180, 1182 and 1184.

[0529] Accordingly, the liquid supply ports 1151 and 1157 and the liquidsupply ports 1164 and 1170 respectively connected to the liquid supplypassages 1148 and 1154 and the liquid supply passages 1160 and 1166formed in the front surface part 1116A and the back surface part 1116Bare bored in the front surface part 1116A of the upper base plate 1116,and further, the liquid supply ports 1179 and 1181 and the liquid supplyports 1183 and 1185 respectively connected through the extensionpassages 1178, 1180, 1182 and 1184 to the liquid supply passages 1118and 1124 and the liquid supply passages 1130 and 1136 formed in thefront surface part 1114A and the back surface part 1114B of the lowerbase plate 1114 are bored. These liquid supply ports 1151, 1157, 1164,1170, 1179, 1181, 1183 and 1185 are disposed alternately in the channelwidth direction, and the opening widths are suitably set within therange of 1 μm to 500 μm. These opening widths are basically set by thesame method as the case of the micromixers 1010, 1086 and 1100 of theeighth embodiment.

[0530] The liquid supply ports 1151, 1157, 1164, 1170, 1179, 1181, 1183and 1185 bored in the base plate 1116 are respectively connected to theliquid incoming port 1066 of the mixing flow passage 1064 formed in themixing plate 1014. By this, the solutions L1 to L8 supplied to theheader parts 1119, 1125, 1131, 1137, 1149, 1155, 1161 and 1167 areintroduced into the mixing flow passage 1064 through the liquid supplyports 1151, 1157, 1164, 1170, 1179, 1181, 1183 and 1185 and the liquidincoming port 1066, and are supplied as the solution LM to the liquidoutgoing pipe through this mixing flow passage 1064.

[0531] According to the micromixer 1110 of this embodiment constitutedas described above, the eight kinds of solutions L1 to L8 aresimultaneously mixed in the mixing flow passage 1064, and after thesesolutions are uniformly mixed, or a required chemical reaction, togetherwith the mixing, is completed, the resultant solution LM can be suppliedto the liquid outgoing pipe connected to the liquid outgoing hole 1080.In the case where the kinds of solutions to be processed by themicromixer 1110 is less than eight kinds, that is, in the case of fiveto seven kinds, both ends of one to three passages of the liquid supplypassages 1118, 1124, 1130, 1136, 1142, 1148, 1154, 1160 and 1166 areclosed according to the kinds of the solutions, so that the solution LMin which five to seven kinds of solutions are mixed by the micromixer1110 can be produced.

[0532] According to the micromixers 1010, 1086 and 1100 of No. 1 and No.2 of the eighth embodiment of the invention as described above, the oneor two liquid supply passages 1036, 1088 and 1102 are formed in thefront surface part 1012A of the base plate 1012, the header parts 1046and 1056 and the microchannel parts 1048 and 1058 in the one or twoliquid supply passages 1044 and 1054 are formed in the back surface part1012B, and the through parts 1050 and 1060 piecing from the bottomportions of the microchannel parts 1048 and 1058 to the front surfacepart 1012A are bored in the base plate 1012, so that with respect to theliquid supply passages 1044 and 1054, it becomes unnecessary to form theheader parts 1046 and 1056 and the microchannel parts 1048 and 1058 inthe front surface part 1012A of the base plate 1012.

[0533] Accordingly, by merely boring the liquid supply ports 1052 and1062 connected to the liquid supply passage 1044 and 1054 in the frontsurface part 1012A of the base plate 1012, it becomes possible tointroduce three or four kinds of solutions L1 to L4 into the mixing flowpassage 1064 formed in the mixing plate 1014 and to diffuse and mixthem.

[0534] According to the micromixer 1110 of No. 2 of the eighthembodiment of the invention, the mixer body 1112 is constituted bysuperposing the two base plates 1114 and 1116, which have substantiallythe same structure as the base plate 1012 in the micromixer 1100 of No.1 of the eighth embodiment, and the mixing plate 1014, so that itbecomes possible to introduce five to eight kinds of solutions L1 to L8into the mixing flow passage 1064 formed in the mixing plate 1014 and todiffuse and mix them.

[0535] Incidentally, in the micromixers 1010, 1086, 1100 and 1110 of No.1 and No. 2 of the eighth embodiment as described above, when pluralkinds of solutions flow in a laminar flow state in the mixing flowpassage 1064, the laminar flows formed of the plural kinds of solutionsare put in a regular arrangement (for example, L1-L2-L3-L1- . . . ) inthe mixing flow passage 1064. However, it is not always necessary to putthe plural kinds of solutions in such a regular arrangement in themixing flow passage 1064, and the plural kinds of solutions may besupplied in the mixing flow passage 1064 so that a laminar flow made ofanother solution always intervenes between predetermined two kinds ofsolutions (for example, L1-L3-L2-L3-L1-L3-L2- . . . ).

[0536] Next, a ninth embodiment of a production apparatus which can beused for a production method of silver halide photographic emulsion ofthe present invention will be described with reference to FIGS. 30 to33.

[0537] The ninth embodiment has a further object to provide a micromixerwhich can effectively suppress stagnancy of a solution in a mixing flowpassage as a space where mixing of plural solutions or a chemicalreaction proceeds.

[0538] To this end, in the micromixer (microreactor) of this embodiment,first, the micromixer is constituted to include a plurality of headerparts respectively receiving fluids from the outside, a plurality offluid supply passages, end parts of which are connected to the pluralityof header parts, a plurality of supply ports provided to be bored alongcircular loci at the other end parts of the plurality of fluid supplypassages and to become substantially concentric with each other, and amixing fluid, one end of which is connected to the plurality of supplyports and in which fluids introduced through the plurality of supplyports flow out from the other end part, wherein opening widths of thesupply ports in an opening width direction orthogonal to the circularloci are formed to be from 1 μm to 500 μm.

[0539] By the constitution as described above, the plural supply portsbored along the circular loci and disposed to be substantiallyconcentric with each other are provided at the other end parts of theplural fluid supply passage, one end part of the mixing flow passage atthe upstream side is connected to these plural supply ports so thatplural kinds of fluids introduced into the mixing flow passages throughthe plural supply ports become lamella-like laminar flows correspondingto the opening widths of the supply ports and flow in the mixing flowpassage, and molecules of the respective fluids mutually diffuse at theinterface between the mutually adjacent laminar flows, and accordingly,when the opening widths of the plural supply ports are made sufficientlyminute widths (from 1 μm to 500 μm), the plural kinds of fluidsintroduced into the mixing flow passage through the plural supply portsare uniformly mixed in a very short time, and a fluid in which theplural kinds of fluids are mixed can be supplied from the liquidoutgoing port of the mixing flow passage to the outside of themicromixer.

[0540] In the micromixer constituted as stated above, when thedownstream side end parts in the plural fluid supply passages and themixing flow passage are linearly disposed, and the mixing flow passageitself is extended linearly, the flow of the fluid in the mixing flowpassage also becomes linear, so that stagnancy of the fluid caused by anabrupt change of the flow in the mixing flow passage does not occur, andwhen the cross-sectional area of the mixing flow passage is madeconstant at an arbitrary position, the stagnancy of the mixed fluidcaused by a change of the cross-sectional area in the mixing flowpassage also does not occur.

[0541] In the micromixer constituted as stated above, as the fluidsupplied to the plural fluid supply passages from the outside, forexample, a liquid, a gas, a solid liquid mixture in which metal fineparticles or the like are dispersed in the liquid, a solid gas mixturein which metal fine particles or the like are dispersed in the gas, or agas liquid mixture in which gas is not dissolved but is dispersed in theliquid also becomes an object, and that the kind of a fluid is differentincludes not only a case where a chemical composition is different, butalso a case where a state of, for example, temperature or a solid liquidratio is different.

[0542] (No. 1 of Ninth Embodiment)

[0543]FIG. 30 shows an example of a micromixer according to No. 1 of theninth embodiment of the invention. The micromixer 2010 is forsimultaneously mixing two kinds of solutions L1 and L2 and supplying asolution LM in which these solutions L1 and L2 are uniformly mixed tothe outside. Here, when the solutions L1 and L2 are mixed by themicromixer 2010, it is conceivable that a chemical reaction occursbetween the solutions L1 and L2 in some case and a reaction does notoccur in another case, and the micromixer of this embodiment can be usedfor both the cases.

[0544] As shown in FIG. 30, the micromixer 2010 is formed to besubstantially cylindrical as a whole, and includes a cylindrical mixerbody 2012 constituting an outer shell part of a device. Here, a straightline S in the drawing indicates the axial center of the device, and adirection along this axial center S is made an axial direction of thedevice in the following description. A base end part of the mixer body2012 in the axial direction is a large diameter part 2014 which is madelarge as compared with a tip side portion, and a pair of first headerpart 2016 and second header part 2018 receiving the solutions L1 and L2from the outside are provided in the large diameter part 2014. A tipside portion of the mixer body 2012 with respect to the large diameterpart is a circular pipe part 2020 the inner diameter of which isconstant, a liquid outgoing port 2022 of the solution LM is bored in thetip end part of this circular pipe part 2020, and a ring-shaped flangepart 2024 is provided at the tip end part of the circular pipe part 2020so as to extend toward the outer peripheral side.

[0545] Here, a liquid outgoing pipe (not shown) provided with a flangepart paired with the flange part 2024 is coupled to the tip end part ofthe mixer body 2012, and the solution LM discharged from the liquidoutgoing port 2022 of the mixer body 2012 is sent to a storage containerfor temporal storage through the liquid outgoing pipe, anothermicromixer for performing a next process to the solution LM, and thelike. Here, the flange part 2024 of the mixer body 2012 and the flangepart of the liquid outgoing pipe can be coupled by various jointstructures, such as a screw joint using a bolt and a nut, or a ferulejoint in which a ring-shaped coupling member is fitted from the outerperipheral side of a pair of flange parts, or may be coupled by welding.

[0546] The base end surface of the large diameter part 2014 in the mixerbody 2012 is closed by a disk-shaped bottom cover 2026, and a circularinsertion hole 2028 is bored in the center of this bottom cover 2026. Around rod straightening member 2030 is coaxially disposed in the mixerbody 2012 so as to protrude from the inside of the large diameter part2014 into the circular pipe part 2020. The base end part of thestraightening member 2030 is inserted into the insertion hole 2028 ofthe bottom cover 2026 and is supported. A conical part 2032 the diameterof which becomes small toward the tip side is formed at the tip end partof the straightening member 2030. Here, the outer diameter of thestraightening member 2030 is smaller than the inner diameter of thecircular pipe part 2020, and a dimension difference with respect to theinner diameter of the circular pipe part 2020 is set on the basis of theflow volumes of the solutions L1 and L2 in the circular pipe part 2020.

[0547] A disk-shaped partition plate 2034 for substantially dividing aspace in the large diameter part 2014 into two equal parts in the axialdirection is disposed in the large diameter part 2014 of the mixer body2012, and a base end side space and a tip end side space divided by thispartition plate 2034 are made a first header part 2016 and a secondheader part 2018. Liquid supply pipes 2036 and 2038 are respectivelyconnected to these header parts 2016 and 2018. Pressurized solutions L1and L2 are supplied through these liquid supply pipes 2036 and 2038 tothe header parts 2016 and 2018 from two liquid supply sources (notshown) installed at the upstream side of the micromixer 2010. Theseliquid supply sources are constituted by, for example, other micromixersfor producing the solutions L1 and L2, or storage tanks for storing thesolutions L1 and L2, and pumps.

[0548] A circular opening part having an opening diameter of anintermediate size between the inner diameter of the circular pipe part2020 and the outer diameter of the straightening member 2030 is bored inthe center of the partition plate 2034, and a pipe-like partition wallmember 2040 protruding from the peripheral fringe part of the openingpart into the circular pipe part 2020 is integrally formed in thepartition plate 2034. This partition wall member 2040 is disposedcoaxially with the circular pipe part 2020 and the straightening member2030, and divides a space between the circular pipe part 2020 and thestraightening member 2030 into an inner peripheral side space and anouter peripheral side space. Here, the outer peripheral side space andthe inner peripheral side space divided by the partition wall member2040 are made a first liquid supply passage 2042 and a second liquidsupply passage 2044, and these first and second liquid supply passages2042 and 2044 respectively communicate with the first and second headerparts 2016 and 2018 at the base end side. A cylindrical space thickerthan the liquid supply passages 2042 and 2044 is formed in the circularpipe part 2020 of the mixer body 2012 at the tip end side of thepartition wall member 2040 and the base end side of the conical part2032 of the straightening member 2030, and this cylindrical space is amixing flow passage 2046 in which mixing or mixing and a chemicalreaction of the solution L1 and the solution L2 supplied from the liquidsupply passages 2042 and 2044 are performed.

[0549] Plural (four in this embodiment) spacers 2048 are providedbetween the inner peripheral surface of the circular pipe part 2020 andthe outer peripheral surface of the partition wall member 2040 in themixer body 2012, and plural (four in this embodiment) spacers 2050 arealso provided between the inner peripheral surface of the partition wallmember 2040 and the outer peripheral surface of the straightening member2030. Each of these plural spacers 2048 and 2050 is formed to have arectangular plate shape, and is supported so that its front and backsurface parts are in parallel with the flow direction (direction of anarrow F) of the solutions L1 and L2 in the circular pipe part 2020. Theplural spacers 2048 and 2050 are disposed at intervals of 90° in thecircumferential direction with the axial center S as the center, and thepositions in the circumferential direction are coincident with eachother. Here, the outer peripheral side spacer 2048 couples the partitionwall member 2040 to the circular pipe part 2020, the inner peripheralside spacer 2050 couples the straightening member 2030 to the partitionwall member 2040, and the opening widths W1 and W2 (see FIG. 30A) of theliquid supply passages 2042 and 2044 in the diameter direction are set.By this, the partition wall member 2040 and the straightening member2030 are coupled and fixed to the circular pipe part 2020 at sufficientstrength, displacement from a predetermined position or deformation bythe influence of liquid pressure of the solutions L1 and L2 or gravityis prevented, and the opening widths W1 and W2 are certainly kept atpreviously set sizes.

[0550] As shown in FIG. 30B, a first liquid supply port 2052 and asecond liquid supply port 2054 opened in the mixing flow passage 2046are formed at the tip end part of the first liquid supply passage 2042and the second liquid supply passage 2044. These liquid supply ports2052 and 2054 are bored along the circular loci with the axial center Sas the center, and are disposed to become concentric with each other.Here, the opening width W1 of the first liquid supply port 2052 in thediameter direction is suitably set within the range of from 1 μm to 500μm in accordance with the supply amount, kind and the like of thesolution L1 to the first header part 2016. The opening width W2 of thesecond liquid supply port 2054 in the diameter direction is alsosuitably set within the range of from 1 μm to 500 μm in accordance withthe supply amount, kind and the like of the solution L2 to the secondheader part 2018.

[0551] Here, the opening widths W1 and W2 respectively define theopening areas of the liquid supply ports 2052 and 2054, and the initialflow rates of the solutions L1 and L2 introduced into the mixing flowpassage 2046 through the liquid supply ports 2052 and 2054 aredetermined in accordance with the opening areas of the liquid supplyports 2052 and 2054 and the supply amounts of the solutions L1 and L2.These opening widths W1 and W2 are set so that for example, the flowrates of the solutions L1 and L2 supplied into the mixing flow passage2046 through the liquid supply ports 2052 and 2054 become equal to eachother. However, in the case where consideration is given to theshortening of the time until the solutions L1 and L2 are uniformlymixed, naturally, it is advantageous to narrow the opening widths W1 andW2, and it is desirable that the thickness of the partition wall member2040 in the diameter direction is also made as thin as possible.

[0552] A space in the circular pipe part 2020 at the tip end side withrespect to the mixing flow passage 2046 is made a liquid outgoingpassage 2056 in which the solution LM flows toward the liquid outgoingport 2022 after the solutions L1 and L2 are mixed in the mixing flowpassage 2046, or mixing and a chemical reaction are performed. Here, inthe case where the solution LM is produced by only the mixing of thesolutions L1 and L2, it is necessary that the solutions L1 and L2 aresubstantially uniformly mixed at the exit part of the mixing flowpassage 2046, and in the case where the solution LM is produced by themixing of the solutions L1 and L2 and the chemical reaction, it isnecessary that the solutions L1 and L2 are substantially uniformly mixedat the exit part of the mixing flow passage 2046 and the chemicalreaction of the solutions L1 and L2 is also substantially perfectlycompleted. Accordingly, it is necessary to set the passage length PF(see FIG. 30A) of the mixing flow passage 2046 in the flow direction ofthe solutions L1 and L2 to such a length that the mixing of thesolutions L1 and L2 is completed or the mixing and the chemical reactionare substantially completed. Incidentally, it is assumed that thesolutions L1 and L2 and the solution LM in which these are mixed arealways closely filled in the mixer body 2012, and flow from the headerparts 2016 and 2018 to the side of the liquid outgoing port 2022.

[0553] In the micromixer 2010 of this embodiment constituted asdescribed above, the pressurized solutions L1 and L2 are supplied to theheader parts 2016 and 2018 through the liquid supply pipes 2036 and2038, and these solutions L1 and L2 are supplied from the header parts2016 and 2018 into the liquid supply passages 2042 and 2044, flow inthese liquid supply passages 2042 and 2044, and are introduced, asliquid flows having predetermined flow rates, into the mixing flowpassage 2046 through the liquid supply port 2052. At this time, sincethe opening widths W1 and W2 of the liquid supply ports 2052 and 2054are made as minute as 1 μm to 500 μm, the solutions L1 and L2 introducedinto the mixing flow passage 2046 through the liquid supply ports 2052and 2054 respectively become lamella-like laminar flows having widthscorresponding to the opening widths W1 and W2, and flow to the side ofthe liquid outgoing passage 2056, and at the interface of the respectivelaminar flows, molecular diffusion occurs in the normal direction andthe solutions L1 and L2 are mixed, and the solutions L1 and L2 areuniformly mixed at the front side of the liquid outgoing passage 2056,or they are uniformly mixed and the chemical reaction between thesolutions L1 and L2 is completed, so that the solution LM is produced.This solution LM flows in the liquid outgoing passage 2056, and issupplied to the liquid outgoing pipe connected to the tip end part ofthe mixer body 2012 through the flange part 2024.

[0554] According to the micromixer 2010 of No. 1 of the ninth embodimentof the invention, the two liquid supply ports 2052 and 2054, which arebored along the circular loci and are disposed to be substantiallyconcentric with each other, are provided at the tip end parts of theplural liquid supply passages 2042 and 2044, and the mixing flow passage2046 is connected to these liquid supply ports 2052 and 2054, so thatthe two kinds of solutions L1 and 12 introduced into the mixing flowpassage through the liquid supply ports 2052 and 2054 becomelamella-like laminar flows corresponding to the opening widths W1 and W2of the liquid supply ports 2052 and 2054 and flow in the mixing flowpassage 2046, and molecules of the respective solutions L1 and L2 aremutually diffused at the interface between the adjacent laminar flows.Accordingly, when the opening widths W1 and W2 of the liquid supplyports 2052 and 2054 are made sufficiently minute (from 1 μm to 500 μm),the two kinds of solutions L1 and L2 introduced into the mixing flowpassage 2046 through the liquid supply ports 2052 and 2054 are uniformlymixed in a short time, and the solution LM obtained after the two kindsof solutions L1 and L2 are mixed or the mixing and the chemical reactionare completed is sent to the liquid outgoing passage 2056, and can besupplied to another micromixer, a storage tank, or the like through theliquid outgoing pipe.

[0555] Further, in the micromixer 2010, since the two liquid supplypassages 2042 and 2044 and the mixing flow passage connected to theliquid supply ports 2052 and 2054 in the liquid supply passages 2042 and2044 are linearly disposed with the axial center S as the center, theredoes not occur stagnancy of the solutions L1, L2 and LM by abrupt changeof flows of the solutions L1, L2 and LM in the mixing flow passage 2046,and since the cross-sectional area of the mixing flow passage 2046 inthe direction orthogonal to the axis is constant at an arbitraryposition, there does not also occur stagnancy of the solutions L1, L2and LM due to the change of the cross-sectional area in the mixing flowpassage 2046. As a result, since it is possible to suppress depositionand aggregation caused by stagnancy of the solutions L1 and L2 and thesolution LM in the micromixer 2010, it becomes possible to preventclogging due to the aggregation or deposition or to prevent reduction ofhomogeneity of a product due to mixing of aggregates or deposits.Incidentally, although the cross-sectional area of the mixing flowpassage 2046 of this embodiment is larger than the total of thecross-sectional area s of the liquid supply passages 2042 and 2044 bythe cross-sectional area of the partition wall member 2040, the innerdiameter of the mixing flow passage 2046 maybe made small relatively tothe inner diameter of the liquid supply port 2052 so that thecross-sectional area of the mixing flow passage 2046 is coincident withthe total of the cross-sectional area s of the liquid supply passages2042 and 2044.

[0556] In the micromixer 2010, the flange part 2024 is provided at thetip end part of the mixer body 2012, and the mixer body 2012 can bedirectly connected to the liquid outgoing pipe having the paired flangepart by using this flange part 2024, so that a specific pipe dedicatedfor a micromixer, for connecting the mixer body 2012 to anothermicromixer disposed at the downstream side, a storage tank or the likecan also be eliminated, and installation to a production line of achemical substance, medicines, or the like becomes easy.

[0557] Next, modified examples of the micromixer of No. 1 of the ninthembodiment of the invention will be described. FIGS. 31 and 32 showmodified examples of the micromixer of No. 1 of the ninth embodiment ofthe invention.

[0558] First, a micromixer 2060 shown in FIG. 31 will be described. Thismicromixer 2060 is for mixing three kinds of solutions L1, L2 and L3 toproduce a solution LM. In the micromixer 2060, a space in a largediameter part 2014 is substantially divided into three equal parts in anaxial direction by two first partition plates 2062 and a secondpartition plate 2064, and three spaces divided by these partition plates2062 and 2064 are made a first header part 2066, a second header part2068 and a third header part 2070 in sequence from abase end side to atip end side. Liquid supply pipes 2036, 2037 and 2038 are respectivelyconnected to these header parts 2066, 2068 and 2070. A pressurizedsolution L1, solution L2 and solution L3 are respectively supplied fromthree liquid supply sources (not shown) installed at the upstream sideof the micromixer 2010 to the header parts 2066, 2068 and 2070 throughthese liquid supply pipes 2036, 2037 and 2038.

[0559] A circular opening part having an opening diameter of anintermediate dimension between an inner diameter of a circular pipe part2020 and an outer diameter of a straightening member 2030 is bored inthe center of the first partition plate 2062, and a pipe-shaped firstpartition wall member 2072 protruding into the circular pipe part 2020from the peripheral part of the opening part is integrally formed in thefirst partition plate 2062. A circular opening part having an openingdiameter of an intermediate dimension between the inner diameter of thefirst partition wall member 2072 and the outer diameter of thestraightening member 2030 is bored also in the center of the secondpartition plate 2064, and a pipe-shaped second partition wall member2074 protruding from the peripheral part of the opening part into theinner peripheral side of the first partition wall member 2072 isintegrally formed in the second partition plate 2062. These partitionwall members 2072 and 2074 are disposed coaxially with the circular pipepart 2020 and the straightening member 2030, and divide a space betweenthe circular pipe part 2020 and the straightening member 2030 into anouter peripheral side space, an intermediate space and an innerperipheral side space in the diameter direction. Here, the outerperipheral side, intermediate, and inner peripheral side spaces dividedby the partition wall member 2040 are made a first liquid supply passage2076, a second liquid supply passage 2078 and a third liquid supplypassage 2080, and these liquid supply passages 2076, 2078 and 2080communicate with the header parts 2066, 2068 and 2070 at the side of thebase end part.

[0560] In the mixer body 2012, plural (four in this embodiment) spacers2082, 2084 and 2086 intervene between the circular pipe part 2020 andthe first partition wall member 2072, between the first partition wallpart 2072 and the second partition wall member 2074, and between thesecond partition wall member 2074 and the straightening member 2030.Each of these plural spacers 2082, 2084 and 2086 is formed to have arectangular plate shape, and is supported so that its front and backsurface parts are in parallel with the flow direction (direction of anarrow F) of the solutions L1 to L3 in the circular pipe part 2020. Thesespacers 2082, 2084 and 2086, similar to the spacers 2048 and 2050 in themicromixer 2010 shown in FIG. 30, couple and fix the first partitionwall member 2072, the second partition wall member 2074, and thestraightening member 2030 to the circular pipe part 2020, and set theopening widths W1, W2 and W3 (see FIG. 31A) of the liquid supplypassages 2076, 2078 and 2080 in the diameter direction. By this, thepartition wall members 2072 and 2074 and the straightening member 2030are coupled and fixed to the circular pipe part 2020 at sufficientstrength, so that displacement from a predetermined position ordeformation by the influence of liquid pressure of the solutions L1 toL3 or the gravity can be prevented, and the opening widths W1, W2 and W3are certainly kept at previously set dimensions.

[0561] As shown in FIG. 31B, a first liquid supply port 2088, a secondliquid supply port 2090 and a third liquid supply port 2092 respectivelyopened in the mixing flow passage 2046 are formed at tip end parts ofthe first liquid supply passage 2076, the second liquid supply passage2078 and the third liquid supply passage 2080. These liquid supply ports2088, 2090 and 2092 are bored along the circular loci with the axialcenter S as the center and are disposed to become concentric with eachother. Here, The opening widths W1, W2 and W3 of the liquid supply ports2088, 2090 and 2092 in the diameter direction, similar to the case ofthe micromixer 2010 shown in FIG. 30, are suitably set within the rangeof from 1 μm to 500 μm in accordance with the supply amounts, kinds andthe like of the solutions L1 to L3 to the header parts 2066, 2068 and2070.

[0562] In the case where the solution LM is produced by only the mixingof the solutions L1 to L3, it is necessary that the solutions L1 and L2are substantially uniformly mixed at the exit part of the mixing flowpassage 2046, and in the case where the solution LM is produced by themixing of the solutions L1 to L3 and a chemical reaction, it isnecessary that the solutions L1 to L3 are substantially uniformly mixedat the exit part of the mixing flow passage 2046, and the chemicalreaction among the solutions L1 to L3 is also substantially perfectlycompleted. Accordingly, it is necessary that the passage length PF (seeFIG. 31A) of the mixing flow passage 2046 in the flow direction of thesolutions L1 to L3 is set to such a length that the mixing of thesolutions L1 to L3 is completed, or the mixing and the chemical reactionare completed.

[0563] In the micromixer 2060 of this embodiment constituted asdescribed above, when the pressurized solutions L1 to L3 are supplied tothe header parts 2066, 2068 and 2070 through the liquid supply pipes2026, 2027 and 2028, these solutions L1 to L3 are supplied from theheader parts 2066, 2068 and 2070 into the liquid supply passages 2076,2078 and 2080, flow in these liquid supply passages 2076, 2078 and 2080,and are introduced, as liquid flows having predetermined flow rates,into the mixing flow passage 2046 through the liquid supply ports 2088,2090 and 2092. At this time, since the opening widths W1, W2 and W3 ofthe liquid supply ports 2088, 2090 and 2092 are made as minute as 1 μmto 500 μm, the three kinds of solutions L1 to L3 introduced into themixing flow passage 2046 through the liquid supply ports 2088, 2090 and2092 become lamella-like laminar flows having widths corresponding tothe opening widths W1, W2 and W3 and flow to the side of the liquidoutgoing passage 2056, and molecular diffusion occurs at the interfaceof the respective laminar flows in the normal direction to mix thesolutions L1 to L3, so that the solution LM is obtained after thesolutions L1 to L3 are uniformly mixed at the front side of the liquidoutgoing passage 2056, or these solutions are uniformly mixed and thechemical reaction among the solutions L1 to L3 is completed. Thissolution LM flows in the liquid outgoing passage 2056, and is suppliedto the liquid outgoing pipe connected to the tip end part of the mixerbody 2012 through the flange part 2024.

[0564] As is apparent from the comparison between the micromixer 2010and the micromixer 2060, according to the constitution of themicromixers 2010 and 2060 of this embodiment, by installing morepartition plates for dividing the large diameter part 2014 in the axialdirection, and more partition wall members integrally formed with thepartition plates and dividing the space between the circular pipe part2020 and the straightening member 2030 in the diameter direction, it ispossible to easily install more header parts to which the solutions aresupplied and more liquid supply passages for supplying the solutions asthe laminar flows into the mixing flow passage 2046. Accordingly, theoperation and effect similar to the micromixer 2010 shown in FIG. 30 areobtained, and it becomes possible to easily realize the micromixer thatmixes four or more kinds of solutions as lamella-like laminar flows inthe mixing flow passage 2046, or mixes them and causes the chemicalreaction to occur.

[0565] Next, a micromixer 2100 shown in FIG. 32 will be described.Similarly to the micromixer 2010 shown in FIG. 30, this micromixer 2100is for mixing two kinds of solutions L1 and L2 to produce a solution LM.This micromixer 2100 is different from the micromixer 2010 in thatspacers 2048 and 2050 disposed between the circular pipe part 2020 andthe partition wall member 2040 and between the partition wall member2040 and the straightening member 2030 are omitted, and instead of thesespacers 2048 and 2050, ring-shaped nozzle plates 2102 and 2104 areattached to opening parts of the liquid supply passages 2042 and 2044 atthe tip end side.

[0566] The two nozzle plates 2102 and 2104 are provided between thecircular pipe part 2020 and the partition wall member 2040 and betweenthe partition wall member 2040 and the straightening member 2030, andare fixed so as to close the opening parts of the liquid supply ports2052 and 2054 at the tip end side. As shown in FIG. 32B, plural circularliquid supply ports 2106 and 2108 are bored in these nozzle plates 2102and 2104, and liquid supply ports 2052 and 2054 communicate with amixing flow passage 2046 through the liquid supply ports 2106 and 2108.The inner diameters R1 and R2 of these liquid supply ports 2106 and 2108are made smaller than the opening widths W1 and W2 of the liquid supplypassages 2042 and 2044. The plural liquid supply ports 2106 are providedin the nozzle plate 2102 so that the pitches in the peripheral directionwith the axial center S as the center become equal to each other, andthe plural liquid supply ports 2108 are also provided in the nozzleplate 2104 so that pitches in the peripheral direction with the axialcenter S as the center become equal to each other. At this time, it isdesired that the liquid supply port 2106 and the liquid supply port 2108are disposed in the nozzle plates 2102 and 2104 as close as possible.

[0567] Here, similarly to the spacers 2048 and 2050 in the micromixer2010, in the nozzle plates 2102 and 2104, the partition wall member 2040and the straightening member 2030 are coupled and fixed to the circularpipe part 2020, and the opening widths of the liquid supply passages2042 and 2044 in the diameter direction are set. By this, the partitionwall member 2040 and the straightening member 2030 are coupled and fixedto the circular pipe part 2020 at sufficient strength, displacement froma predetermined position or deformation by the influence of liquidpressure of the solutions L1 and L2 or the gravity can be prevented, andthe opening widths of the liquid supply passages 2042 and 2044 can becertainly kept at previously set size. The inner diameter R1 of theliquid supply port 2106 in the nozzle plate 2102 is suitably set withinthe range of from 1 μm to 500 μm in accordance with the supply amount,kind and the like of the solution L1, and further, the number of theliquid supply ports 2106 in the nozzle plate 2102 is determined inaccordance with the inner diameter R1 and the supply amount of thesolution L1 to the first header part 2016. The inner diameter R2 of theliquid supply port 2108 in the nozzle plate 2104 is also suitably setwithin the range of from 1 μm to 500 μm in accordance with the supplyamount, kind and the like of the solution L2 to the second header part2018, and further, the number of the liquid supply ports 2108 in thenozzle plate 2104 is determined in accordance with the inner diameter R2and the supply amount of the solution L2 to the second header part 2018.

[0568] In the micromixer 2100 of this embodiment constituted asdescribed above, when the pressurized solutions L1 and L2 are suppliedto the header parts 2016 and 2018 through the liquid supply pipes 2036and 2038, these solutions L1 and L2 are supplied from the header parts2016 and 1018 into the liquid supply passages 2042 and 2044, flow inthese liquid supply passages 2042 and 2044, and are introduced as liquidflows having predetermined flow rates into the mixing flow passage 2046through the liquid supply ports 2106 and 2108. At this time, since theinner diameters R1 and R2 of the liquid supply ports 2106 and 2108 areas minute as 1 μm to 500 μm, the two kinds of solutions L1 and L2introduced into the mixing flow passage 2046 through the liquid supplyports 2106 and 2108 respectively become plural thin rod-shaped laminarflows having outer diameters corresponding to the inner diameters R1 andR2 and flow to the side of the liquid outgoing passage 2056, and at theinterface of the respective laminar flows, molecular diffusion occurs inits normal direction and the solutions L1 and L2 are mixed, and thesolutions L1 and L2 are uniformly mixed at the front side of the liquidoutgoing passage 2056, or they are uniformly mixed and the chemicalreaction between the solutions L1 and L2 is completed, so that thesolution LM is obtained. This solution LM flows through the liquidoutgoing passage 2056, and is supplied to the liquid outgoing pipeconnected to the tip end part of the mixer body 2012.

[0569] In the micromixer 2100 shown in FIG. 32, the solutions L1 and L2are introduced into the mixing flow passage 2046 through the circularliquid supply ports 2106 and 2108, these solutions L1 and L2 are dividedinto the plural thin rod-shaped laminar flows and flow in the mixingflow passage 2046. On the other hand, in the micromixer 2010 shown inFIG. 30, each of the solutions L1 and L2 becomes a single lamella-likelaminar flow, and flows in the mixing flow passage 2046. Accordingly, inthe micromixer 2100, as compared with the micromixer 2010 shown in FIG.30, in addition to the same operation and effect as the micromixer 2010,it becomes possible to increase specific surface areas concerning thelaminar flows respectively formed by the solutions L1 and L2 in themixing flow passage 2046, and it becomes possible to shorten the timeuntil the solutions L1 and L2 are uniformly mixed in the mixing flowpassage 2046, or the time until the chemical reaction is completed.

[0570] In the micromixer 2100 shown in FIG. 32, although the liquidsupply ports 2106 and 2108 in the nozzle plates 2102 and 2104 are madecircular, the shapes of these liquid supply ports 2106 and 2108 are notnecessarily required to be circular, and an arbitrary shape, such as afan shape widening toward the outer peripheral side, a hexagon, or anellipse, can be used, and the specific surface areas of the laminarflows formed by the solutions L1 and L2 discharged from the liquidsupply ports 2106 and 2108 may be adjusted by changing the shapes of theliquid supply ports 2106 and 2108.

[0571] In the micromixers 2010, 2060 and 2100 of this embodiment asdescribed above, although the respective liquid supply ports 2052, 2054,2088, 2090, 2092, 2106 and 2108 are bored along the circular loci, it isnot necessarily required to bore these liquid supply ports 2052, 2054,2088, 2090, 2092, 2106 and 2108 along the circular loci, and may bebored along annular loci other than the circle, such as a rectangularannular shape, an elliptical annular shape, or an oblong annular shape.Alternatively, the liquid supply ports 2052, 2054, 2088, 2090, 2092,2106 and 2108 may be made zigzag-shaped, such as a continuous wavy shapeor conical shape to substantially increase the areas of the contactinterfaces among the solutions L1 to L3.

[0572] (No. 2 of the Ninth Embodiment)

[0573]FIG. 33 shows a micromixer of No.2 of the ninth embodiment of theinvention. Incidentally, this micromixer 2120 is based on the micromixer2060 (see FIG. 31) of No. 1 of the ninth embodiment, and additionallyincludes liquid temperature control devices 2122, 2124 and 2126 forcontrolling the liquid temperature of the solutions L1 to L3 and thesolution LM. Therefore, in the micromixer 2120 shown in FIG. 33, membershaving the same structure and operation as the micromixers 2010 and 2060of No. 1 of the ninth embodiment are designated by the same symbols andthe descriptions are omitted.

[0574] The micromixer 2120 of No. 1 and No. 2 of the ninth embodiment,similar to the micromixer 2060 shown in FIG. 31, is for mixing threekinds of solutions L1, L2 and L3 or for mixing thereof and effecting achemical reaction to produce the solution LM, and this is especiallysuitable for the case where the chemical reaction accompanies the mixingof the solutions L1 to L3. As shown in FIG. 33B, the micromixer 2120 isprovided with a first liquid temperature control device 2122, a secondliquid temperature control device 2124, and a third liquid temperaturecontrol device 2126 using liquids having relatively large heatcapacities, such as water or oil, as heat transfer media C1, C2 and C3,respectively. Here, the liquid temperature control devices 2122 and 2124are for mainly controlling the liquid temperatures of the solutions L1to L3 which are flowing in the mixing flow passage 2046 and in whichmixing or mixing and a chemical reaction are proceeding, and the liquidtemperature control device 2126 is for controlling the liquidtemperature of the solution LM flowing in a liquid outgoing passage2056.

[0575] The first liquid temperature control device 2122 includes astraightening member 2128 disposed at the center of a mixer body 2012,and a first heat exchanger (not shown). The straightening member 2128,similar to the straightening member 2030 of No. 1 of the ninthembodiment, has a substantially cylindrical outer shape in which aconical part 2130 is formed at a tip end part. However, differently fromthe straightening member 2030 that has a solid shape, an outer shellpart is formed of a thin metal plate, and an inner part is hollow. Aliquid supply pipe 2132 having a diameter smaller than an inner diameterof the straightening member 2128 is inserted into the straighteningmember 2128 from its base end side, and the liquid supply pipe 2132 issupported coaxially with the straightening member 2128 by a closingplate (not shown) for closing an opening of the straightening member2128 at the base end side and plural spacers 2134.

[0576] The tip end of the liquid supply pipe 2132 reaches the vicinityof the root of the conical part 2130, and a liquid supply port 2133 forsupplying the heat transfer medium C1 into the straightening member 2128is bored in the tip end surface. In the straightening member 2128, thegap formed between its inner peripheral surface and the outer peripheralsurface of the liquid supply pipe 2132 is a return current passage 2136of the heat transfer medium C1, and the heat transfer medium C1 flowingout from the liquid supply port 2133 of the liquid supply pipe 2132flows through this return flow passage 2136 from the tip end side of thestraightening member 2128 to the base end side.

[0577] Here, a liquid return pipe (not shown) is coupled to the closingplate for closing the base end surface of the liquid supply pipe 2132,and the tip end part of this liquid return pipe communicates with thereturn flow passage 2136. In addition, the base end part of the liquidreturn pipe and the base end part of the liquid supply pipe 2132 arerespectively connected to a first heat exchanger (not shown), and thisfirst heat exchanger adjusts the temperature of the heat transfer mediumC1 returned from the straightening member 2128 through the liquid returnpipe to a previously set liquid temperature T1, and sends out it intothe straightening member 2128 through the liquid supply pipe 2132.

[0578] A circulation pump (not shown) is provided in the first liquidtemperature control device 2122, and this pump always circulates theheat transfer medium C1 between the heat exchanger and the straighteningmember 2128 through the liquid supply pipe 2132 and the liquid returnpipe. In the case where there is a temperature difference between theliquid temperature T1 of the heat transfer medium C1 flowing in thereturn flow passage 2136 and the liquid temperature of the solution L3flowing in the third liquid supply passage 2080, or the liquidtemperatures of the solutions L1 to L3 which flow in the mixing flowpassage 2046 and in which the mixing is proceeding, the heat exchange isperformed between the heat transfer medium C1 and the solution L3 or thesolutions L1 to L3 through the outer shell part of the straighteningmember 2128, and the temperature change is made so that the liquidtemperature of the solution L3 or the liquid temperatures of thesolutions L1 to L3 approach the liquid temperature T1.

[0579] The second liquid temperature control device 2124 includes a heatexchange jacket 2138 disposed at the outer peripheral side of the mixingflow passage 2046 in the circular pipe part 2020 and a second heatexchanger (not shown) The heat exchange jacket 2138 has a thickcylindrical outer shape, and is fixed to the mixer body 2012 so that itsinner peripheral surface comes in close contact with the outerperipheral surface of the circular pipe part 2020. The inside of theheat exchange jacket 2138 is made hollow, and this inner space is made acircular liquid chamber 2140 in which the heat transfer medium C2 flows.End parts of the liquid supply pipe 2142 and the liquid return pipe 2144are respectively connected to the heat exchange jacket 2138, and theother end parts of the liquid supply pipe 2142 and the liquid returnpipe 2144 are respectively connected to a second heat exchanger (notshown).

[0580] The second heat exchanger adjusts the temperature of the heattransfer medium C2 returned from the heat exchange jacket 2138 throughthe liquid return pipe 2144 to a previously set liquid temperature T2,and sends out it into the circular liquid chamber 2140 of the heatexchange jacket 2138 through the liquid supply pipe 2142. This heattransfer medium C2 flows in the circular liquid chamber 2140, passesthrough the liquid return pipe 2144 and returns to the second heatexchanger. A partition wall (not shown) for restricting the flowdirection of the heat transfer medium C2 is installed in this circularliquid chamber 2140, and by this partition wall, after the heat transfermedium C2 makes at least one round in the circulation liquid chamber2140, it reaches the liquid return pipe 2144.

[0581] The second temperature control device 2124, similar to the firstliquid temperature control device 2122, also includes a pump forcirculation (not shown), and this pump always circulates the heattransfer medium C2 between the second heat exchanger and the circulationliquid chamber 2140 through the liquid supply pipe 2142 and the liquidreturn pipe 2144. Therefore, in the case where there is a temperaturedifference between the liquid temperature T2 of the heat transfer mediumC2 flowing in the circulation liquid chamber 2140 and the liquidtemperature of the solutions L1 to L3 which flow in the mixing flowpassage 2046 and in which the mixing is proceeding, the heat exchange isperformed between the heat transfer medium C2 and the solutions L1 to L3through the inner peripheral wall part of the heat exchange jacket 2138and the outer peripheral wall part of the circular pipe part 2020, andthe temperature change occurs so that the liquid temperature of thesolutions L1 to L3 approach the liquid temperature T2.

[0582] The third liquid temperature control device 2126 includes a heatexchange jacket 2146 disposed at the outer peripheral side of the liquidoutgoing passage 2056 in the circular pipe part 2020, and a third heatexchanger (not shown). The heat exchange jacket 2146 has the same shapeand structure as the heat exchange jacket 2138, and a circulation liquidchamber 2148 in which the heat transfer medium C3 flows is provided inits inside. End parts of the liquid supply pipe 2150 and the liquidreturn pipe 2152 are respectively connected to the heat exchange jacket2146, and the other end parts of the liquid supply pipe 2150 and theliquid return pipe 2152 are respectively connected to the second heatexchanger (not shown).

[0583] The third heat exchanger adjusts the temperature of the heattransfer medium C3 returned from the heat exchange jacket 2146 throughthe liquid return pipe 2152 to a previously set liquid temperature T3,and sends out it into the circulation liquid chamber 2148 of the heatexchange jacket 2138 through the liquid supply pipe 2150. This heattransfer medium C3 flows in the circulation liquid chamber 2148, passesthrough the liquid return pipe 2152, and returns to the third heatexchanger. A partition wall (not shown) for restricting the flowdirection of the heat transfer medium C3 is installed in thiscirculation liquid chamber 2148, and by this partition wall, after theheat transfer medium C3 makes at least one round in the circulationliquid chamber 2148, it flows to reach the liquid return pipe 2152.

[0584] The third liquid temperature control device 2126, similar to thefirst liquid temperature control device 2122, also includes acirculating pump (not shown), and this pump always circulates the heattransfer medium C3 between the third heat exchanger and the circulationliquid chamber 2148 through the liquid supply pipe 2150 and the liquidreturn pipe 2152. Therefore, in the case where there is a temperaturedifference between the liquid temperature T3 of the heat transfer mediumC3 flowing in the liquid circulation chamber 2148 and the liquidtemperature of the solution LM flowing in the liquid outgoing passage2056, heat exchange is performed between the heat transfer medium C3 andthe solution LM through the inner peripheral wall part of the heatexchange jacket 2146 and the outer peripheral wall part of the circularpipe part 2020, and the temperature change occurs so that the liquidtemperature of the solution LM approaches the liquid temperature T3.

[0585] Next, the operation of the micromixer 2120 of this embodimentconstituted as described above will be described. In the micromixer2120, when the pressurized solutions L1 to L3 are supplied to the headerparts 2066, 2068 and 2070 through the liquid supply pipes 2026, 2027 and2028, these solutions L1 to L3 are supplied from the header parts 2066,2068 and 2070 into the liquid supply passages 2076, 2078 and 2080, flowin these liquid supply passages 2076, 2078 and 2080, and are introducedas liquid flows having predetermined flow rates into the mixing flowpassage 2046 through the liquid supply ports 2088, 2090 and 2092. Atthis time, since the opening widths W1, W2 and W3 of the liquid supplyports 2088, 2090 and 2092 are made as minute as 1 μm to 500 μm, thethree kinds of solutions L1 to L3 introduced into the mixing flowpassage 2046 through the liquid supply ports 2088, 2090 and 2092 becomelamella-like laminar flows having widths corresponding to the openingwidths W1, W2 and W3 and flow toward the side of the liquid outgoingpassage 2056, and at the interface of the respective laminar flows,molecular diffusion occurs in the normal direction and the solutions L1to L3 are mixed, and the solutions L1 to L3 are uniformly mixed at thefront side of the liquid outgoing passage 2056, or they are mixed and achemical reaction among the solutions L1 to L3 is completed, so that thesolution LM is obtained. This solution LM flows through the liquidoutgoing port 2056, and is supplied to the liquid outgoing pipeconnected to the tip end part of the mixer body 2012.

[0586] In the micromixer 2120 of this embodiment, the liquid temperatureT1 of the heat transfer medium C1 is suitably set, so that the liquidtemperature of the solution L3 flowing in the third liquid supplypassage 2080 can be raised, kept or lowered by the first liquidtemperature control device 2122, and accordingly, the liquid temperatureof the solution L3 supplied into the mixing flow passage 2046 throughthe third liquid supply port 2092 can be controlled to a desiredtemperature. Further, in the micromixer 2120, the liquid temperatures T1and T2 of the heat transfer media C1 and C2 are suitably set, so thatthe liquid temperatures of the solutions L1 to L3 which flow in themixing flow passage 2046 and in which the mixing proceeds or the mixingand a chemical reaction proceed can be raised, kept or lowered by theliquid temperature control devices 2122 and 2124. At this time, in thecase where the chemical reaction accompanies the mixing of the solutionsL1 to L3, and the rate of the chemical reaction, the property of areaction product, and the like are influenced by the liquid temperaturesof the solutions L1 to L3, the reaction rate of the chemical reactionaccompanying the mixing of the solutions L1 to L3, the property of thereaction product and the like can be precisely controlled. Further, inthe micromixer 2120, the liquid temperature T3 of the heat transfermedium C3 is suitably set, so that the liquid temperature of thesolution LM flowing in the liquid outgoing passage 2056 can be raised,kept or lowered by the third liquid temperature control device 2126. Atthis time, in the case where also after the completion of a primarychemical reaction of the solutions L1 to L3, a secondary reaction suchas coalescence, growth or decomposition of the product continuouslyoccurs in the solution LM, and the secondary reaction is influenced bythe liquid temperature of the solution LM, it becomes possible toprecisely control the reaction rate, the property of the reactionproduct and the like in the secondary reaction.

[0587] In the micromixer 2120 of this embodiment, although the liquidtemperature control devices 2122, 2124 and 2126 are such that liquidsare made the heat transfer media C1, C2 and C3, and the liquidtemperatures of the solutions L1 to L3 or that of the solution LM iscontrolled by the heat exchange with these heat transfer media C1, C2,and C3, instead of these liquid temperature control devices 2122, 2124and 2126, for example, a Peltier element is disposed at the inside ofthe straightening member 2128 or the outer peripheral side of thecircular pipe part 2020, and heat exhaust from and heat supply to thesolutions L1 to L3 or the solution LM may be performed by the Peltierelement. In the case where the liquid temperatures of the solutions L1to L3 or that of the solution LM has only to be raised, a heatgenerating resistor such as a halogen heater is disposed in the insideof the straightening member 2128 or at the outer peripheral side of thecircular pipe 2020, and the liquid temperature may be raised.

[0588] Next, a tenth embodiment of a production apparatus which can beused for a production method of silver halide photographic emulsion ofthe invention will be described with reference to FIGS. 34 to 36.

[0589] The tenth embodiment has a further object to provide a micromixerin which the mixing of fluids introduced into a mixing flow passagethrough plural supply ports and the progress of a chemical reaction caneffectively accelerated and can be controlled with sufficiently highaccuracy.

[0590] Thus, in the micromixer (microreactor) of this embodiment, first,the micromixer includes plural fluid supply passages in each of which afluid supplied from the outside flows from one end part to the other endpart, plural supply ports respectively bored at the other end parts ofthe plural fluid supply passages and disposed to be adjacent to eachother in a predetermined diffusion direction orthogonal to the flowdirection of the fluids in the fluid supply passage, a mixing flowpassage one end part of which is connected to the plural supply portsand which discharges the fluids from the other end part, the fluidsbeing introduced through the plural supply ports, and diffusion controlmeans for transmitting a mechanical vibration in the diffusion directionto the fluids flowing in the mixing flow passage, and opening widths ofthe plural supply ports in the diffusion direction are from 1 μm to 500μm.

[0591] By the construction as described above, the plural supply portsare provided which are bored in the other end parts of the plural fluidsupply passages and are disposed to be adjacent to each other in thepredetermined diffusion direction orthogonal to the flow direction ofthe fluids in the fluid supply passages, the one end part of the mixingflow passage at the upstream side is connected to these plural supplyports, the diffusion control means transmits the vibration in thediffusion direction to the fluids flowing in the mixing flow passage, sothat the plural kinds of fluids introduced into the mixing flow passagethrough the plural supply ports become lamella-like laminar flowscorresponding to the opening widths of the supply ports and flow in themixing flow passage, the movement of minute fluid bodies in thediffusion direction is accelerated at the interface between the adjacentlaminar flows, and molecular movement of the respective fluids isincreased, and accordingly, when the opening widths of the plural supplyports are respectively made sufficiently minute widths (from 1 μm to 500μm), the plural kinds of fluids introduced into the mixing flow passagethrough the plural supply ports can be efficiently mixed by the movementof the minute fluid bodies. Further, since the molecular movements ofthe fluids flowing in the mixing flow passage can be increased mainly inthe diffusion direction among the fluids by the vibration from thediffusion control means, the movement of molecules in the diffusiondirection is increased in the vicinity of the contact interface betweenthe laminar flows formed by the fluids, and the mixing between thefluids in the mixing flow passage and the chemical reaction accompanyingthe mixing can be efficiently accelerated.

[0592] As a result, by suitably controlling the frequency, the intensity(vibration energy) and the like of the vibration transmitted to thefluids by the diffusion control means in accordance with the kind,liquid temperature, viscosity, flow rate and the like of the fluidsintroduced into the mixing flow passage, it becomes possible toprecisely control the progress of the mixing between the fluids in themixing flow passage and the progress of the chemical reactionaccompanying the mixing. Here, to control the progress of the mixing andthe progress of the chemical reaction mainly mean the mixing rate amongthe fluids and the chemical rate, and in the case where the chemicalreaction accompanies the mixing of the fluids, it also includes thecontrol of properties of the reaction product, such as the shape andsize, and the control of acceleration and suppression of the coalescenceor flocculation of the reaction product.

[0593] Second, instead of the diffusion control means for transmittingthe vibration in the diffusion direction to the fluids flowing in themixing flow passage in the first micromixer, diffusion control means forirradiating the fluids flowing in the mixing flow passage with amicrowave in the diffusion direction is provided to constitute themicromixer.

[0594] By the constitution as described above, since the molecularmovement of the fluids flowing in the mixing flow passage can beincreased mainly in the diffusion direction between the fluids by themicrowave irradiated from the diffusion control means, similarly to thefirst micromixer of this embodiment, it is possible to increase thediffusion rate of a molecule in the vicinity of the contact interfacebetween the laminar flows formed by the fluids, and to efficientlyaccelerate the mixing between the fluids in the mixing flow passage andthe chemical reaction accompanying the mixing.

[0595] As a result, by suitably controlling the frequency, the intensity(electromagnetic energy) and the like of the microwave irradiated to thefluids by the diffusion control means in accordance with the kind,liquid temperature, viscosity, flow rate and the like of the fluidsintroduced into the mixing flow passage, it becomes possible toprecisely control the progress of the mixing between the fluids in themixing flow passage and the progress of the chemical reactionaccompanying the mixing.

[0596] In the second micromixer, since the molecular movement of thefluids is increased by the microwave with high directionality, itbecomes possible to concentratedly increase the molecular movement ofthe fluids existing in a specific region of the micro flow passage, andas compared with the first micromixer of this embodiment, it becomespossible to control the progress of the mixing between the fluids in themixing flow passage and the progress of the chemical reactionaccompanying the mixing with higher accuracy.

[0597] Incidentally, in the first and second micromixers, as the fluidssupplied from the outside to the plural fluid supply passages, forexample, a liquid, a gas, a solid liquid mixture in which metal finegrains or the like are dispersed in liquid, a solid gas mixture in whichmetal fine grains are dispersed in gas, or a gas liquid mixture in whichgas is not dissolved in liquid but is dispersed therein also becomes anobject, and that the kind of fluid is different includes not only a casewhere a chemical composition is different, but also a case where thestate of, for example, temperature or a solid liquid ratio or the likeis different.

[0598] (No. 1 of the Tenth Embodiment)

[0599]FIG. 34 shows an example of a micromixer of this embodiment. Thismicromixer 3010 is for mixing two kinds of solutions L1 and L2 and forsupplying a solution LM in which these solutions L1 and L2 are uniformlymixed to the outside. When the solutions L1 and L2 are mixed by themicromixer 3010, it is conceivable that a chemical reaction occursbetween the solutions L1 and L2 in some case and a chemical reactiondoes not occur in another case, and the micromixer of this embodimentcan be used for both the cases.

[0600] As shown in FIG. 34, the outer shape of the micromixer 3010 isformed into a substantially prismatic shape as a whole, and includes athin tubular body 3012 constituting an outer shell part of the device.Here, a straight line Sin the drawing indicates an axial centerconnecting the centers of cross-sections of the mixer body 3012. Thecross-section of the mixer body 3012 in the direction orthogonal to theaxis is rectangular, and a partition wall plate 3014 dividing an innerspace of the mixer body 3012 is disposed in the mixer body 3012 at thebase end side (left side in FIG. 34) in the axial direction. Thispartition wall plate 3014 substantially divides the space in the mixerbody 3012 into two equal parts in the short side direction of thecross-section, so that, a first liquid supply passage 3016 and a secondliquid supply passage 3018 linearly extending in the axial direction areformed in the mixer body 3012.

[0601] As shown in FIG. 34A, a base end part of the mixer body 3012 isclosed by a cover plate 3020, and two liquid supply pipes 3038 and 3039are connected to this cover plate 3020. The pressurized solutions L1 andL2 are supplied into the liquid supply passages 3016 and 3018 throughthese liquid supply pipes 3038 and 3039 from two liquid supply sources(not shown) installed at the upstream side of the micromixer 3010. Theseliquid supply sources are constituted by, for example, other micromixersfor producing the solutions L1 and L2, storage tanks storing thesolutions L1 and L2, pumps and the like.

[0602] As shown in FIG. 34B, a first liquid supply port 3022 and asecond liquid supply port 3024, each being substantially rectangular,are bored in the tip end surfaces of the two liquid supply passages 3016and 3018 in the mixer body 3012, and these liquid supply ports 3022 and3024 are adjacent to each other in the diffusion direction (direction ofan arrow D) of the solutions L1 and L2. Here, the diffusion direction isa direction orthogonal to the flow direction (direction of an arrow F)of the solutions L1 and L2 in the liquid supply passages 3016 and 3018,and is coincident with the short side direction in the cross-sectionorthogonal to the axis of the mixer body 3012 in this embodiment. Eachof the liquid supply ports 3022 and 3024 has a thin and long rectangularshape in an interface direction (direction of an arrow B) orthogonal tothe diffusion direction.

[0603] As shown in FIG. 34A, in the mixer body 3012, a prismatic spacewhere the liquid supply passages 3016 and 3018 meet each other is formedin the flow direction at the downstream side of the liquid supplypassages 3016 and 3018, and this space is a mixing flow passage 3026 inwhich the mixture of the solutions L1 and L2 supplied from the liquidsupply passages 3016 and 3018 or the chemical reaction accompanying themixture is performed. In this mixing flow passage 3026, the end part atthe upstream side in the flow direction is connected to the liquidsupply ports 3022 and 3024, and the end part at the downstream sidecommunicates with the liquid outgoing port 3028 bored in the tip endsurface of the mixer body 3012. An annular flange part 3030 is providedat the tip end part of the mixer body 3012 to extend toward the outerperipheral side of the liquid outgoing port 3028.

[0604] Here, the opening width W1 of the first liquid supply port 3022in the diffusion direction is suitably set within the range of from 1 μmto 500 μm in accordance with the supply amount, kind and the like of thesolution L1 to the first liquid supply passage 3016. The opening widthW2 of the second liquid supply port 3024 in the diffusion direction issuitably set within the range of from 1 μm to 500 μm in accordance withthe supply amount, kind and the like of the solution L2 to the secondliquid supply passage 3018. The opening width WB of the liquid supplyports 3022 and 3024 in the interface direction is set to at least thesize of the opening widths W1 and W2. These opening widths W1, W2 and WBdefine the opening areas of the liquid supply ports 3022 and 3024, andinitial flow rates of the solutions L1 and L2 introduced into the mixingflow passage 3026 through the liquid supply ports 3022 and 3024 aredetermined in accordance with the opening areas of the liquid supplyports 3022 and 3024 and the supply amounts of the solutions L1 and L2.Among these opening widths W1, W2 and WB, the opening widths W1 and W2are set so that, for example, the flow rates of the solutions L1 and L2supplied through the liquid supply ports 3022 and 3024 into the mixingflow passage 3026 become equal to each other. However, whenconsideration is given to the shortening of the time until the solutionsL1 and L2 are uniformly mixed, naturally, it is advantageous to narrowthe opening widths W1 and W2, and it is also desired that the thicknessof the partition wall plate 3014 in the diffusion direction is made asthin as possible.

[0605] In the micromixer 3010, the mixture of the solutions L1 and L2 isperformed in the mixing flow passage 3026, or the mixture and thechemical reaction are performed, and the obtained solution LM isdischarged from the liquid outgoing port 3028. In the case where thesolution LM is produced only by the mixture of the solutions L1 and L2,it is necessary that the solutions L1 and L2 are substantially uniformlymixed at the exit part of the mixing flow passage 3026, and in the casewhere the solution LM is produced by the mixture of the solutions L1 andL2 and the chemical reaction, it is necessary that the solutions L1 andL2 are substantially uniformly mixed at the exit part of the mixing flowpassage 3026 and the chemical reaction between the solutions L1 and L2is also substantially perfectly completed. Accordingly, it is necessarythat the passage length PF (see FIG. 34A) of the mixing flow passage3026 in the flow direction is set to such a length that the mixture ofthe solutions L1 and L2 is completed, or the mixture and the chemicalreaction are completed. It is assumed that the solutions L1 and L2 andthe solution LM in which these are mixed are always closely filled inthe mixer body 3012, and flow in the liquid supply passages 3016 and3018 toward the side of the liquid outgoing port 3028.

[0606] Here, a liquid outgoing pipe (not shown) having a flange partpaired with the flange part 3030 is coupled to the tip end part of themixer body 3012, and the solution LM discharged from the liquid outgoingport 3028 of the mixer body 3012 is sent through the liquid outgoingpipe to a storage container for temporal storage, another micromixer forperforming a next process to the solution LM, and the like. The flangepart 3030 of the mixer body 3012 and the flange part of the liquidoutgoing pipe can be coupled by various joint structures, such as ascrew joint using a bolt and a nut, or a ferule joint in which aring-shaped coupling member is inserted from the outer peripheral sideof the pair of flange parts, or may be coupled by welding. As the liquidoutgoing pipe, as long as the flange part provided at the downstream endpart is conformable to the shape of the flange part 3030 of themicromixer 3010, a general cylindrical metal pipe or the like canbemused.

[0607] Thick plate-shaped vibration generators 3032 are attached to anupper surface part and a lower surface part of the mixer body 3012 atthe downstream side so as to adhere closely thereto. The length of thepair of vibration generators 3032 is substantially equal to the lengthof the mixing flow passage 3026 in the flow direction, and the width inthe interface direction is substantially equal to the opening width ofthe mixing flow passage 3026. Here, the vibration generator 3032 isdisposed so that its upstream side end coincides with the upstream sideend of the mixing flow passage 3026. Therefore, this, the pair ofvibration generators 3032 correctly face the whole of the upper surfacepart and the whole of the lower surface part in the mixing flow passage3026. A vibration part 3034 is provided in the vibration generator 3032at the adherence surface to the mixer body 3012, and this vibration part3034 transmits a mechanical vibration with a predetermined frequency tothe solutions L1 and L2 in the mixing flow passage 3026 and the solutionLM through the mixer body 3012 at the time of driving the vibrationgenerator 3032. At this time, the vibration from the vibration part 3034is transmitted to the solutions L1 and L2 and the solution LM in thediffusion direction as indicated by an arrow V of FIG. 34, and themolecular movement of the solutions L1, L2 and LM is increased in thediffusion direction by this transmitted vibration, so that the mixturebetween the solutions L1 and L2 or the chemical reaction accompanyingthe mixture is accelerated.

[0608] The vibration generator 3032 uses, for example, a piezoelectricelement as a vibration generating source, and by supplying an alternatecurrent to the piezoelectric element, the mechanical vibrationcorresponding to the current frequency is generated from the vibrationpart 3034. At this time, the vibration frequency generated from thevibration part 3034 is controlled within the range of 1 KHz to 10 MHz,that is, within the band of a high frequency and an ultrasonic wave.Specifically, mainly, when the solutions L1 and L2 flowing in the mixingflow passage 3026 are mixed or mixed and chemically reacted, thevibration frequency is suitably set in accordance with a desired mixturerate or chemical reaction rate of the solutions L1 and L2. At this time,when consideration is not given to the resonance effect in the mixerbody 3012 in which the vibration is transmitted and in the solutions L1,L2 and LM, in general, as the vibration frequency becomes high, thevibration energy (kinetic energy) becomes high. Accordingly, the mixtureof the solutions L1 and L2 in the mixing flow passage 3026 and theprogress of the chemical reaction are accelerated.

[0609] As shown in FIG. 34A, the micromixer 3010 is provided with adrive control part 3036 for controlling the driving of the pair ofvibration generators 3032. When the solutions L1, L2 and LM flow in themixing flow passage 3026, this drive control part 3036 controls the onand off state of the vibration generators 3032, the duty ratio as aratio of an on time to an off time, and the vibration frequency inaccordance with a control condition previously set in an internal memoryor the like. The control condition varies according to the kinds of thesolutions L1 L2, that is, the chemical composition, liquid temperature,viscosity, etc. of the solutions L1 and L2, and the property of areaction product in the case where the chemical reaction accompanies themixture of the solutions L1 and L2. This control condition also variesaccording to the change of the supply amounts of the solutions L1 andL2, that is, the flow rates of the solutions L1 and L2 in the mixingflow passage 3026. Such a control condition is set, for example, throughan operation terminal or the like operated by an operator of aproduction line in which the micromixer 3010 is disposed, or isautomatically set by a host process computer for controlling the wholeproduction line on the basis of a production schedule or the like.

[0610] In the micromixer 3010 constituted as stated above, thepressurized solutions L1 and L2 are supplied to the liquid supplypassages 3016 and 3018 through the liquid supply pipes 3038 and 3039, sothat these solutions L1 and L2 flow in the liquid supply passages 3016and 3018, and are introduced as the liquid flows having predeterminedflow rates into the mixing flow passage 3026 through the liquid supplyports 3022 and 3024. At this time, since the opening widths W1 and W2 ofthe liquid supply ports 3022 and 3024 are made as minute as 1 μm to 500μm, the solutions L1 and L2 introduced into the mixing flow passage 3026through the liquid supply ports 3022 and 3024 become lamella-likelaminar flows having widths corresponding to the opening widths W1 andW2 and flow toward the side of the liquid outgoing port 3028, and at thecontact interface of the respective laminar flows, the moleculardiffusion occurs in the normal direction, and the mixture of thesolutions L1 and L2 proceeds. At the same time, in the micromixer 3010,since the mechanical vibration from the pair of vibration generators3032 is transmitted to the solutions L1, L2 and LM in the mixing flowpassage 3026 in the diffusion direction, the movement of minute fluidbodies of the solutions L1 and L2 flowing in the mixing flow passage3026 and the molecular movement in the diffusion direction can beincreased by the transmitted vibration, and therefore, the movement rateof the molecule in the diffusion direction and in the vicinity of thecontact interface between the laminar flows formed by the solutions L1and L2 can be increased, and the mixture of the solutions L1 and L2 inthe mixing flow passage 3026 and the chemical reaction accompanying themixing can be efficiently accelerated.

[0611] Accordingly, according to the micromixer 3010 of this embodiment,the frequency and the like of the vibration transmitted to the solutionsL1, L2 and LM by the vibration generator 3032 are suitably controlled inaccordance with the kind, liquid temperature, viscosity and the like ofthe solutions L1 and L2 introduced into the mixing flow passage 3026, sothat the mixing between the solutions L1 and L2 in the mixing flowpassage 3026 and the progress of the chemical reaction accompanying themixing can be precisely controlled. As a result, it becomes possible tocontrol the mixing rate of the solutions L1 and L2 and the chemicalreaction rate to desired rates, and especially in the case where thechemical reaction accompanies the mixing between the solutions L1 andL2, the mixing rate and the reaction rate are precisely controlled, orthe vibration is transmitted also to the reaction product in thesolutions L1, L2 and LM, so that it becomes also possible to control theproperties such as the shape or size of the reaction product, and tocontrol the acceleration and suppression of the coalescence orflocculation of the reaction product.

[0612] In the micromixer 3010, since the mixing and the chemicalreaction between the solutions L1 and L2 in the mixing flow passage 3026can be accelerated by the vibration from the vibration generator 3032,as compared with the case where the vibration generator 3032 does notexist, the passage length PF of the mixing flow passage 3026 necessaryfor uniformly mixing the solutions L1 and L2 or completing the chemicalreaction accompanying the mixing can be shortened and the device can beminiaturized.

[0613] It is not necessary to always drive the vibration generator 3032at the time of supply of the solutions L1 and L2 to the mixing flowpassage 3026, and in the case where the chemical reaction between thesolutions L1 and L2 is desired to be slowly performed, the driving ofthe vibration generator 3032 maybe stopped. The mixer body 3012 isformed of stainless having high mechanical stability and less vibrationdamping, or metal material such as copper, titanium alloy, aluminumalloy, gold or platinum, and further, in view of the corrosionresistance, a contact part with the solutions L1, L2 and LM may becoated or plated with other material such as glass or ceramics. In thecase where the mixer body 3012 can not be made sufficiently thin, ormust be formed of a material having high vibration damping, an openingpart is formed in the mixer body 3012 to face the mixing flow passage3026, and the vibration generator 3032 may be disposed so that theoscillation part 3034 is inserted into the mixing flow passage 3026 fromthis opening part.

[0614] Next, a modified example of the micromixer of No. 1 of the tenthembodiment of the invention will be described. FIG. 35 shows a modifiedexample of the micromixer of No. 1 of the tenth embodiment of theinvention. In structure, a micromixer 3040 shown in FIG. 35 is differentfrom the micromixer 3010 shown in FIG. 34 only in that three vibrationgenerators 3042, 3044 and 3046 are attached to a mixer body 3012, andthe number of vibration generators is increased, and the structures ofthe micromixers 3010 and 3040 in other points are made common. Thestructures themselves of the vibration generators 3042, 3044 and 3046are also made common to the vibration generator 3032.

[0615] As described above, the vibration generators 3042, 3044 and 3046are attached to the mixer body 3012 so as to adhere closely to each ofthe upper surface part and the lower surface part at the downstreamside. These vibration generators 3042, 3044 and 3046 are adjacent toeach other in the flow direction, the length in the flow direction ismade approximately ⅓ of the mixing flow passage 3026, and the width inthe interface direction is made substantially equal to the opening widthof the mixing flow passage 3026. Here, the vibration generators aredisposed such that the upstream end of the vibration generator 3042disposed at the most upstream side coincides with the upstream end ofthe mixing flow passage 3026, and the downstream end of the vibrationgenerator 3046 disposed at the most downstream side substantiallycoincides with the downstream end of the mixing flow passage 3026.Therefore, the upper and lower three vibration generators 3042, 3044 and3046 correctly face the whole of the upper surface part and the whole ofthe lower surface part in the mixing flow passage 3026.

[0616] As shown in FIG. 35A, a drive control part 3048 for controllingthe driving of the vibration generators 3042, 3044 and 3046 are providedin the micromixer 3040. When the solutions L1, L2 and LM flow in themixing flow passage 3026, this drive control part 3048 controls the onand off state of the vibration generators 3042, 3044 and 3046, the dutyratio as a ratio of an on time to an off time, and the vibrationfrequency to comply with the control condition previously set in theinternal memory or the like. At this time, the drive control part 3048can control the vibration generators 3042, 3044 and 3046 located atdifferent positions in the flow direction in accordance with differentcontrol conditions.

[0617] The control conditions set in the drive control part 3036,basically similar to the micromixer 3010 shown in FIG. 34, vary with thekinds of the solutions L1 and L2, that is, the chemical composition,liquid temperature, viscosity, etc. of the solutions L1 and L2, and theproperties of a reaction product, etc. in the case where the chemicalreaction accompanies the mixing of the solutions L1 and L2. In addition,the control conditions vary with the change of the supply amounts of thesolutions L1 and L2, that is, the flow rates of the solutions L1 and L2in the mixing flow passage 3026. Such control conditions are set, forexample, through an operation terminal or the like operated by anoperator of a production line in which the micromixer 3010 is disposed,or is automatically set by a host process computer for controlling thewhole production line on the basis of a production schedule or the like.

[0618] In the micromixer 3040 constituted as set forth above, thepressurized solutions L1 and L2 are supplied to the liquid supplypassages 3016 and 3018 through the liquid supply pipes 3038 and 3039,and similarly to the micromixer 3010 shown in FIG. 34, the solutions L1and L2 introduced into the mixing flow passage 3026 through the liquidsupply ports 3022 and 3024 become lamella-like laminar flows havingwidths corresponding to the opening widths W1 and W2, and flow towardthe side of the liquid outgoing port 3028, and at the contact interfaceof the laminar flows, the movement of minute fluid bodies is acceleratedin the normal direction, the molecular motion is increased, and themixing of the solutions L1 and L2 proceeds, and at the same time, themechanical vibration from the vibration generators 3042, 3044 and 3046is transmitted to the solutions L1, L2 and LM in the mixing flow passage3026 in the diffusion direction, whereby the movement rates of themolecules of the solutions L1 and L2 in the mixing flow passage 3026 areincreased and the mixing and the chemical reaction accompanying themixing can be efficiently accelerated.

[0619] Further, in the micromixer 3040, since the vibration generators3042, 3044 and 3046 disposed at different positions in the flowdirection can be driven under different control conditions, thevibration transmitted to the solutions L1 and L2 and the solution LMflowing in the mixing flow passage 3026 can be changed stepwise in theflow direction. As a result, since the mixing of the solutions L1 and L2in the mixing flow passage 3026 or the chemical reaction accompanyingthe mixing can be accelerated under different vibration conditionscorrespondingly to the three vibration generators 3042, 3044 and 3046,as compared with the micromixer 3010 shown in FIG. 34, the mixing of thesolutions L1 and L2 in the mixing flow passage 3026 and the progress ofthe chemical reaction accompanying the mixing can be preciselycontrolled.

[0620] Incidentally, at the time of supply of the solutions L1 and L2 tothe mixing flow passage 3026, it is not necessary to simultaneouslydrive all of the three vibration generators 3042, 3044 and 3046, and oneof the three vibration generators 3042, 3044 and 3046 may be selectivelydriven or its driving may be stopped. In the micromixers 3010 and 3040of this embodiment, although the vibration generators 3032, 3042, 3044and 3046 having the piezoelectric elements as the vibration generatingsources are used, any vibration generating source may be used as long asa mechanical vibration of approximately 1 KHz to 10 MHz can begenerated, and for example, an eccentric cam driven by a motor, anelectromagnetic actuator, an air pressure actuator or the like may beused as a vibration generating source. In the micromixers 3010 and 3040of this embodiment, in order to change the intensity (vibration energy)of the vibration transmitted to the solutions L1, L2 and LM in themixing flow passage 3026, the frequency of the vibration generated bythe vibration generators 3032, 3042, 3044 and 3046 is changed, however,the vibration energy may be changed by changing the amplitude of thevibration.

[0621] (No. 2 of the Tenth Embodiment)

[0622]FIG. 36 shows a micromixer of No. 2 of the tenth embodiment of theinvention. This micromixer 3110, similar to the micromixers 3010 and3040 of No. 1 of the tenth embodiment, is for simultaneously mixing twokinds of solutions L1 and L2 and for supplying a solution LM to theoutside, in which these solutions L1 and L2 are uniformly mixed or thechemical reaction accompanying the mixing is completed.

[0623] As shown in FIG. 36, the micromixer 3110 is formed to besubstantially cylindrical as a whole, and includes a cylindrical mixerbody 3112 constituting an outer shell part of the device. A straightline S in the drawing indicates the axial center of the device, and adirection along this axial center is made an axial direction of thedevice in the following description. A base end part of the mixer body3112 in the axial direction is made a large diameter part 3114 having alarge diameter as compared with a portion at the tip end side, and apair of first header part 3116 and second header part 3118 which receivethe supply of the solutions L1 and L2 from the outside are provided inthe large diameter part 3114. In the mixer body 3112, a portion at thetip end side with respect to the large diameter part is made a circularpipe part 3120 having a constant inner diameter, a liquid outgoing port3122 of the solution LM is bored in the tip end surface of this circularpipe part 3120, and a ring-shaped flange part 3124 is provided at thetip end part of the circular pipe part 3120 so as to extend to the outerperipheral side of the liquid outgoing port 3122.

[0624] A liquid outgoing pipe (not shown) having a flange part pairedwith the flange part 3124 is coupled to the tip end part of the mixerbody 3112, and the solution LM discharged from the liquid outgoing port3122 of the mixer body 3112 is sent through the liquid outgoing pipe toa storage container for temporal storage or another micromixer forperforming a next process to the solution LM. The flange part 3124 ofthe mixer body 3112 and the flange part of the liquid outgoing pipe canbe coupled by various joint structures, such as a screw joint using abolt and a nut, or a ferule joint in which a ring-shaped coupling memberis fitted from the outer peripheral side of the pair of flange parts, ormay be coupled by welding.

[0625] A base end surface of the large diameter part 3114 in the mixerbody 3112 is closed by a disk-shaped cover plate 3126, and a circularinsertion hole 3128 is bored in the center of this cover plate 3126. Around rod-shaped straightening member 3130 is coaxially disposed in themixer body 3112 so as to protrude from the large diameter part 3114 intothe circular pipe part 3120. A base end part of the straightening member3130 is inserted into the insertion hole 3128 of the cover plate 3126and is supported. A conical part 3132 shrinking in diameter toward thetip end side is formed at the tip end part of the straightening member3130. The outer diameter of the straightening member 3130 is madesmaller than the inner diameter of the circular pipe part 3120, and asize difference between the outer diameter and the inner diameter ofthis circular pipe part 3120 is set on the basis of the flow volumes ofthe solutions L1 and L2 in the circular pipe part 3120.

[0626] A disk-shaped partition plate 3134 for substantially dividing aspace in the large diameter part 3114 into two equal parts in the axialdirection is disposed in the large diameter part 3114 of the mixer body3112, and a base end side space and a tip end side space divided by thispartition plate 3134 are respectively made a first header part 3116 anda second header 3118. Liquid supply pipes 3136 and 3138 are connected tothese header parts 3116 and 3118. The pressurized solution L1 andsolution L2 are supplied to the header parts 3116 and 3118 through theseliquid supply pipes 3136 and 3138 from two liquid supply sources (notshown) installed at the upstream side of the micromixer 3110. Theseliquid supply sources comprises, for example, other micromixers forproducing the solutions L1 and L2, storage tanks for storing thesolutions L1 and L2, pumps and the like.

[0627] A circular opening part having an opening diameter of anintermediate size between the inner diameter of the circular pipe part3120 and the outer diameter of the straightening member 3130 is bored inthe center of the partition plate 3134, and a pipe-shaped partition wallmember 3140 protruding from the peripheral part of the opening part intothe circular pipe part 3120 is integrally formed on the partition plate3134. The partition wall member 3140 are disposed coaxially with thecircular pipe part 3120 and the straightening member 3130, and dividesthe space between the circular pipe part 3120 and the straighteningmember 3130 into an inner peripheral side space and an outer peripheralside space. Here, the outer peripheral side and inner peripheral sidespaced divided by the partition wall member 3140 are respectively made afirst liquid supply passage 3142 and a second liquid supply passage3144, and these first and second liquid supply passage 3142 and 3144communicate with the first and second header parts 3116 and 3118 at thebase end side. In the circular pipe part 3120 of the mixer body 3112, aspace of a cylindrical shape made thick with respect to the liquidsupply passages 3142 and 3144 is formed at the tip end side of thepartition wall member 3140 and at the base end side of the conical part3132 of the straightening member 3130, and this cylindrical space ismade a mixing flow passage 3146 in which the mixing of the solution L1and the solution L2 supplied from the liquid supply passages 3142 and3144 or the mixing and the chemical reaction are performed.

[0628] In the mixer body 3112, plural (four in this embodiment) spacers3148 are provided between the inner peripheral surface of the circularpipe part 3120 and the outer peripheral surface of the partition wallmember 3140, and plural (four in this embodiment) spacers 3150 areprovided between the inner peripheral surface of the partition wallmember 3140 and the straightening member 3130. These plural spacers 3148and 3150 are respectively formed into rectangular plate shapes, and aresupported so that its front and back surface parts become parallel withthe flow direction (direction of an arrow F) of the solutions L1 and L2in the circular pipe part 3120. The plural spacers 3148 and 3150 aredisposed at intervals of 90° in the peripheral direction with the axialcenter S as the center, and the positions in the peripheral directionare coincident with each other. Here, the spacer 3148 at the outerperipheral side couples the partition wall member 3140 to the circularpipe part 3120, and the spacer 3150 at the inner peripheral side couplesthe straightening member 3130 to the partition wall member 3140, andsets the opening widths W1 and W2 (see FIG. 36A) of the liquid supplypassages 3142 and 3144 in the diameter direction. Therefore, thepartition wall member 3140 and the straightening member 3130 are coupledand fixed to the circular pipe part 3120 at sufficient strength, so thatthe displacement from a predetermined position or deformation by theinfluence of liquid pressure of the solutions L1 and L2 or the gravitycan be prevented, and the opening widths W1 and W2 can be certainly keptat previously set sizes.

[0629] As shown in FIG. 36B, a first liquid supply port 3152 and asecond liquid supply port 3154 opened in the mixing flow passage areformed at the tip end parts of the first liquid supply passage 3142 andthe second liquid supply passage 3144. These liquid supply ports 3152and 3154 are bored along circular loci with the axial center S as thecenter and are disposed to be concentric to each other. Here, theopening width W1 of the first liquid supply port 3152 in the diameterdirection is suitably set within the range of from 1 μm to 500 μm inaccordance with the supply amount, kind, etc. of the solution L1 to thefirst header part 3116. In addition, the opening width W2 of the secondliquid supply port 3154 in the diameter direction is also suitably setwithin the range of from 1 μm to 500 μm in accordance with the supplyamount, kind, etc. of the solution L2 to the second header part 3118.

[0630] Here, the opening widths W1 and W2 define the opening areas ofthe liquid supply ports 3152 and 3154, and initial flow rates of thesolutions L1 and L2 introduced into the mixing flow passage 3146 throughthe liquid supply ports 3152 and 3154 are determined in accordance withthe opening areas of the liquid supply ports 3152 and 3154 and thesupply amounts of the solutions L1 and L2. These opening widths W1 andW2 are set such that for example, the flow rates of the solutions L1 andL2 supplied into the mixing flow passage 3146 through the liquid supplyports 3152 and 3154 become equal to each other. However, in the casewhere consideration is given to the shortening of the time until thesolutions L1 and L2 are uniformly mixed, naturally, it is advantageousto narrow the opening widths W1 and W2, and it is desired that thethickness of the partition wall member 3140 in the diameter direction ismade as thin as possible.

[0631] A space at a tip end side relative to the mixing flow passage3146 in the circular pipe part 3120 is made a liquid outgoing passage3156 in which the solution LM, which is obtained after the solutions L1and L2 are mixed or the mixing and the chemical reaction are performedin the mixing flow passage 3146, flows to the liquid outgoing port 3122.Here, in the case where the solution LM is produced only by the mixingof the solutions L1 and L2, it is necessary that the solutions L1 and L2are substantially uniformly mixed at the exit part of the mixing flowpassage 3146, and in the case where the solution LM is produced by themixing of the solutions L1 and L2 and the chemical reaction, it isnecessary that the solutions L1 and L2 are substantially uniformly mixedat the exit part of the mixing flow passage 3146 and the chemicalreaction of the solutions L1 and L2 are also substantially perfectlycompleted. Accordingly, it is necessary that the passage length PF (seeFIG. 36A) of the mixing flow passage 3146 in the flow direction of thesolutions L1 and L2 is set so that the mixing of the solutions L1 and L2is completed, or the mixing and the chemical reaction are substantiallycompleted. Incidentally, it is assumed that the solutions L1 and L2 andthe solution LM in which these are mixed are always closely filled inthe mixer body 3112, and flow from the header parts 3116 and 3118 to theside of the liquid outgoing port 3122.

[0632] As shown in FIG. 36A, plural opening parts 3158 are provided inthe circular pipe part 3120 of the mixer body 3112 so as to face themixing flow passage 3146. These opening parts 3158 are provided atportions corresponding to an upstream part, an intermediate part and adownstream part of the mixing flow passage 3146 in the flow direction,and are disposed at intervals of 90° in the peripheral direction withthe axial center S as the center. Accordingly, in the circular pipe part3120, four opening parts 3158 are provided at each of placescorresponding to the upstream part, the intermediate part and thedownstream part of the mixing flow passage 3146, and twelve openingparts 3158 are provided in total. Plural microwave generators 3160 areattached on the outer peripheral surface of the circular pipe part 3120to correspond to the opening parts 3158. A cylindrical protrusioninsertion part 3162 is provided at the inner peripheral side of each ofthe microwave generators 3160, and in the microwave generator 3160, theinsertion part 3162 is inserted into the opening part 3158, and the tipend surface of the insertion part 3162 is exposed in the mixing flowpassage 3146.

[0633] The microwave generator 3160 irradiates the solutions L1, L2 andLM in the mixing flow passage 3146 with a microwave from the tip endsurface of the insertion part 3162 at the time of driving. At this time,the microwave from the microwave generator 3160 is irradiated to thesolutions L1 and L2 and the solution LM in the diameter directioncoincident with the diffusion direction of the solutions L1 and L2 asindicated by a dotted line of FIG. 36. Since the molecular motion of thesolutions L1, L2 and LM is increased in the diffusion direction by thismicrowave, the mixing of the solutions L1 and L2 or the chemicalreaction accompanying the mixing is accelerated.

[0634] The microwave generator 3160 uses, for example, a magnetron as agenerating source of the microwave, and by supplying a driving currentto this magnetron, the microwave having intensity corresponding to thecurrent value is generated. At this time, as the microwave generated bythe microwave generator 3160, one having a frequency of 10 MHz or moreis selected. Specifically, a frequency of the microwave is selected suchthat the molecular movement of the solutions L1, L2 and LM can beefficiently increased without causing an excessive heating phenomenon inthe solutions L1, L2 and LM flowing in the mixing flow passage 3146.

[0635] As shown in FIG. 36A, a drive control part 3164 for controllingthe drive of the microwave generator 3160 is provided in the micromixer3110. When the solutions L1, L2 and LM flow in the mixing flow passage3146, this drive control part 3164 controls the on/off state of themicrowave generator 3160, and the intensity of the microwave to complywith a control condition previously set in an internal memory or thelike. The control condition varies basically with the kinds of thesolutions L1 and L2, that is, the chemical compositions, liquidtemperature, viscosity, etc. of the solutions L1 and L2, and theproperty etc. of a reaction product in the case where the chemicalreaction accompanies the mixing of the solutions L1 and L2. The controlcondition varies according to the change of the supply amounts of thesolutions L1 and L2, that is, the flow rates of the solutions L1 and L2in the mixing flow passage 3146. Such a control condition is set, forexample, through an operation terminal etc. operated by an operator of aproduction line in which the micromixer 3110 is disposed, or isautomatically set by a host computer for controlling the wholeproduction line on the basis of a production schedule or the like. Thedrive control part 3164 can control the microwave generators 3160located at different positions in the flow direction in accordance withdifferent control conditions.

[0636] In the micromixer 3110 of this embodiment constituted as setforth above, similarly to the micromixer 3010 and 3040 of No.1 of thetenth embodiment, the two kinds of solutions L1 and L2 introduced intothe mixing flow passage 3146 through the liquid supply ports 3152 and3154 become lamella-like laminar flows corresponding to the openingwidths W1 and W2 of the liquid supply ports 3152 and 3154 and flow inthe mixing flow passage 3146, and molecules of the solutions L1 and L2diffuse mutually at the interface of the adjacent laminar flows, so thatthe two kinds of solutions L1 and L2 introduced into the mixing flowpassage 3146 can be uniformly mixed in a short time, or the chemicalreaction accompanying the mixing can be completed, and the obtainedsolution LM can be supplied to the outside. At this time, since themicrowave from the microwave generator 3160 is irradiated to thesolutions L1, L2 and LM in the mixing flow passage 3146, the diffusionrate of molecules of the solutions L1 and L2 in the mixing flow passage3146 is increased and the mixing and the chemical reaction accompanyingthe mixing can be efficiently accelerated.

[0637] Further, in the micromixer 3110, since the microwave generators3160 disposed at different positions in the flow direction can be drivenunder different control conditions, the microwave irradiated to thesolutions L1 and L2 and the solution LM flowing in the mixing flowpassage 3146 can be changed stepwise in the flow direction. As a result,since the mixing of the solutions L1 and L2 in the mixing flow passage3146 or the chemical reaction accompanying the mixing can be acceleratedunder different vibration conditions correspondingly to the microwavegenerators 3160 located at different positions, the mixing of thesolutions L1 and L2 in the mixing flow passage 3146 and the progress ofthe chemical reaction accompanying the mixing can be preciselycontrolled. At this time, since the microwave has high directionality ascompared with the mechanical vibration, it is possible to suppress thesolutions L1, L2 and LM existing in a region corresponding to themicrowave generator 3160 located at a certain position in the flowdirection from receiving the influence of the microwave from themicrowave generator 3160 located at another position. As a result, ascompared with the micromixers 3010 and 3040, the mixing of the solutionsL1, L2 and LM in the mixing flow passage 3146 and the chemical reactionaccompanying the mixing can be further precisely controlled.

[0638] Although the micromixers 3010, 3040 and 3110 of Nos. 1 and 2 ofthe tenth embodiment described above are for mixing or mixing andchemically reacting the two kinds of solutions L1 and L2 in the mixingflow passages 3026 and 3146, also in a micromixer for mixing or mixingand chemically reacting three or more kinds of solutions in the mixingflow passage, the mixing of the solutions and the chemical reaction canbe accelerated by applying the mechanical vibration or microwave to thethree or more kinds of solutions flowing in the mixing flow passage, andthe mixing of the solutions or the progress of the chemical reaction inthe mixing flow passage can be precisely controlled by suitablycontrolling the vibration generator or the microwave generator.

[0639] First, according to the invention, in a production method ofsilver halide photographic emulsion, at least one of a nucleus formingprocess, a nucleus growing process, a chemical sensitizing process, anda spectral sensitizing process are carried out by utilizing the processby using a microreactor. In this method, there is an effect that whenviewed microscopically, the nucleus forming process for bonding a singlesilver ion and a single halogen ion in one-to-one correspondence iscarried out by using a minute region of the microreactor, and a reactionfor suitably forming desired nuclei can be accurately carried out.Alternatively, there is an effect that nuclei of silver halide newlysupplied to grow grains (host grains) of nuclei of silver halide formedby the nucleus forming process are made to uniformly meet the grains(host grains) of the nuclei of silver halide to allow to react eachother, conditions from the meeting of the grains (host grains) of thenuclei of silver halide and the nuclei of newly supplied silver halideat the same timing to the end of the reactions are made uniform, and thegrains (host grains) of the nuclei of silver halide can be uniformlygrown. Alternatively, there is an effect that each crystal lattice inthe single nucleus of silver halide is accurately doped with apredetermined number (for example, one molecule for each crystallattice) of molecules for chemical sensitization, and the sensitizingprocess is performed, so that it is possible to prevent a crystallattice which is not doped with the molecule for chemical sensitizationfrom being formed, to prevent a crystal lattice which is excessivelydoped with the molecule for chemical sensitization from being formed,and to prevent a molecule for chemical sensitization from being inexcess, and it is possible to prevent the agent for chemicalsensitization from wasting. Alternatively, there is an effect that thespectral sensitizing process is performed in which one layer ofmolecules of a spectral sensitizing agent is uniformly adsorbed on thesurface of the single nucleus (grain) of silver halide, so that it ispossible to prevent the generation of a nucleus (grain) of silver halideon which the molecule for spectral sensitization is not adsorbed, toprevent the generation of a nucleus (grain) of silver halide in anadsorption state in which molecules for spectral sensitization areexcessive (multi-molecule adsorption state in which multi-layermolecules of the spectral sensitizing agent are adsorbed on the surfaceof the nucleus (grain) of silver halide), or to prevent the molecule forspectral sensitization from being in excess, and it is possible toprevent the agent for spectral sensitization from wasting.

[0640] As stated above, there is an effect that the silver halidephotographic emulsion having a uniform emulsion property can be producedby the microreactor. Further, there is an effect that since themicroreactor is used, a small production system can be easily scaled upto a mass production system, and the emulsion can be produced at anoptimum production scale corresponding to a required productionquantity.

[0641] Second, according to the invention, in a production method of asilver halide photographic emulsion, when at least one of a nucleusforming process, a nucleus growing process, a chemical sensitizingprocess, and a spectral sensitizing process is performed, a temperaturecontrol of a process liquid is carried out by using a microreactorincluding temperature control means of the process liquid.

[0642] Accordingly, in the case where the temperature control isexecuted by introducing the process liquid into the microreactor havingthe temperature control means for controlling the process liquids toperform heat transfer, since the thermal energy is transmitted in astate where the process liquids form thin layers and the quantitythereof is very small, a temperature changes rapidly to an objective settemperature. Thus, in the case where the temperature control is executedby the microreactor having the temperature control means for controllingthe process liquids, since it can be said that the timing of temperaturechange does not deviate between infinitesimal liquid chemicals forproducing an emulsion forming thin layers, there is an effect that it ispossible to prevent occurrence of difference in the liquid chemicals forproducing the emulsion to be produced due to the difference in thehistory of the temperature change. Further, in the case where thetemperature control is executed by the microreactor having thetemperature control means for controlling the temperature of the processliquid, the thermal energy is transferred to the infinitesimal liquidchemicals for producing an emulsion forming the thin layers and flowingin the inside of the microreactor having the temperature control meansfor controlling the temperature of the process liquid, and thetemperature change of the liquid chemicals for producing the emulsion iscompleted. Thus, in the case where the temperature control is executedby the microreactor having the temperature control means for controllingthe temperature of the process liquid, there is an effect that a waitingtime from the start of the temperature change of the liquid chemicalsfor producing the emulsion to the completion is eliminated, and thewhole process time can be greatly shortened. In addition, in the casewhere the temperature control is executed by the microreactor having thetemperature control means for controlling he temperature of the processliquids, the rate of the temperature change of the liquid chemicals forproducing the emulsion is high (good responsiveness to the temperaturechange), and there is no stagnancy and no recycling flow, so that thereis an effect that the control operation of the temperature to the liquidchemicals for producing the emulsion can be precisely controlled, andthe suitable silver halide photographic emulsion can be produced.

[0643] Since the microreactor is used, there is an effect that a smallproduction system can be easily scaled up to a mass production system,and the emulsion production is enabled at an optimum production scalecorresponding to a required production quantity.

[0644] Third, according to the invention, a production apparatus ofsilver halide photographic emulsion is constituted such that afterprocess liquids processed by using plural microreactors for performing anucleus forming process are collected, the process liquids are suppliedto a next process through a liquid guiding pipe, and are distributed andsupplied through the liquid guiding pipe to plural microreactorsconnected to the liquid guiding pipe, having processing capacityequivalent to all of the plural microreactors for performing the nucleusforming process, and for performing a nucleus growing process, and afterprocess liquids processed by using the plural microreactors forperforming the nucleus forming process are collected, the processliquids are supplied to a next process through a liquid guiding pipe,and the process liquids are distributed and supplied to pluralmicroreactors to be subjected to a chemical sensitizing process or aspectral sensitizing process.

[0645] By doing this, when each of the nucleus forming process, thenucleus growing process, the chemical sensitizing process and thespectral sensitizing process is ended and started, the collection anddistribution of the process liquids is repeated, so that the liquidchemicals for producing the emulsion processed in the respectivemicroreactors are mutually mixed and made uniform at end points ofrespective processes, and accordingly, there is an effect that thequality and performance of the finally produced silver halidephotographic emulsion can be made uniform.

[0646] Further, the production apparatus of the silver halidephotographic emulsion constituted in this series of lines, the number ofthe predetermined plural microreactors installed in each process issuitably set in accordance with the processing capacity or the like, sothat there is an effect that the flow rate of the liquid chemicals forproducing the emulsion between the respective processes becomesconstant, and the whole production system can be constituted such thatthe process liquid does not stagnate and the process can be efficientlyperformed.

[0647] Furthermore, there is an effect that the silver halidephotographic emulsion having uniform emulsion characteristics can beproduced by the microreactors.

[0648] Fourth, according to the invention, in a production apparatus ofa silver halide photographic emulsion, process liquids sent to asubsequent process for effecting the subsequent process, from pluralmicroreactors for performing at least one process in pluralmicroreactors for performing a nucleus forming process, pluralmicroreactors for performing a nucleus growing process, pluralmicroreactors for performing a chemical sensitizing process, and pluralmicroreactors for performing a spectral sensitizing process, arecollected and are temporarily stored in a storage tank, and the processliquids are distributed and supplied from the storage tank to pluralmicroreactors for effecting the subsequent process.

[0649] By doing this, there is an effect that it is possible to proceedwith the operation in such a way that the process liquids aretemporarily stored in the storage tank at the point of time when thenucleus forming process, the nucleus growing process, the chemicalsensitizing process, or the spectral sensitizing process in theproduction process of the silver halide photographic emulsion isperformed, and a subsequent process is performed at a suitable point oftime thereafter. In addition, since the process liquids processed by theplural microreactors provided in parallel are respectively collected inthe storage tank, are blended and can be used, there is an effect thatthe process liquids, which are collected in the storage tank, are mixed,and have the same characteristics, are distributed and supplied to theplural microreactors provided in parallel, and the uniform silver halidephotographic emulsion can be produced.

[0650] Furthermore, since the microreactors are used, there is an effectthat a small production system can be easily scaled up to a massproduction system, and the emulsion can be produced at an optimumproduction scale corresponding to a required production quantity.

What is claimed is:
 1. A production method of silver halide photographicemulsion, comprising a nucleus forming process, a nucleus growingprocess, a chemical sensitizing process, and a spectral sensitizingprocess, wherein at least one of the nucleus forming process, thenucleus growing process, the chemical sensitizing process, and thespectral sensitizing process is performed by using a microreactor.
 2. Aproduction method of silver halide photographic emulsion according toclaim 1, wherein the nucleus forming process is performed by bringing anaqueous halide solution into contact with a silver nitrate solution in asate of at least one laminar flow to form silver halide grain nuclei. 3.A production method of silver halide photographic emulsion according toclaim 2, wherein the nucleus forming process, the nucleus growingprocess, the chemical sensitizing process, or the spectral sensitizingprocess is performed in the presence of gelatin or chemically modifiedgelatin.
 4. A production method of silver halide photographic emulsionaccording to claim 3, wherein at least one of the nucleus formingprocess, the nucleus growing process, the chemical sensitizing process,and the spectral sensitizing process is performed by using at least twomicroreactors.
 5. A production method of silver halide photographicemulsion according to claim 4, wherein a surface of a process liquidflow passage in the microreactor is formed of a material selected fromthe group consisting of nickel, aluminum, silver, gold, platinum,tantalum, stainless, hastelloy, titanium, fine ceramics, specialceramics, and plastic.
 6. A production method of silver halidephotographic emulsion, comprising a nucleus forming process, a nucleusgrowing process, a chemical sensitizing process, and a spectralsensitizing process, wherein when at least one of the nucleus formingprocess, the nucleus growing process, the chemical sensitizing process,and the spectral sensitizing process is carried out, temperature controlof a process liquid is executed by using a microreactor including atemperature control means for controlling the temperature of the processliquid.
 7. A production method of silver halide photographic emulsionaccording to claim 6, wherein the nucleus forming process is performedby bringing an aqueous halide solution into contact with a silvernitrate solution in a state of at least one laminar flow to form silverhalide grain nuclei.
 8. A production method of silver halidephotographic emulsion according to claim 7, wherein the nucleus formingprocess, the nucleus growing process, the chemical sensitizing process,or the spectral sensitizing process is performed in the presence ofgelatin or chemically modified gelatin.
 9. A production method of silverhalide photographic emulsion according to claim 8, wherein at least oneof the nucleus forming process, the nucleus growing process, thechemical sensitizing process, and the spectral sensitizing process isperformed by using at least two microreactors.
 10. A production methodof silver halide photographic emulsion according to claim 9, wherein asurface of a process liquid flow passage in the microreactor is formedof a material selected from the group consisting of nickel, aluminum,silver, gold, platinum, tantalum, stainless, hastelloy, titanium, fineceramics, special ceramics, and plastic.
 11. A production apparatus ofsilver halide photographic emulsion, which performs a nucleus formingprocess, a nucleus growing process, a chemical sensitizing process or aspectral sensitizing process, comprising: a first liquid guiding pipethat collects process liquids processed by using plural microreactorsfor performing the nucleus forming process, and thereafter feeds theliquids to a next process; a second liquid guiding pipe which isconnected to the first liquid guiding pipe for distributing andsupplying the process liquids to plural microreactors which has aprocessing capacity equivalent to all of the processing capacities ofthe plural microreactors for performing the nucleus forming process forperforming the nucleus growing process; a third liquid guiding pipewhich collects the process liquids processed by using the pluralmicroreactors for performing the nucleus growing process, and thereafterfeeds the process liquids to a next process; and a fourth liquid guidingpipe for distributing and supplying the process liquids for the chemicalsensitizing process or the spectral sensitizing process to pluralmicroreactors.
 12. A production apparatus of silver halide photographicemulsion according to claim 11, wherein the nucleus forming process isperformed by bringing an aqueous halide solution into contact with asilver nitrate solution in a state of at least one laminar flow to formsilver halide grain nuclei.
 13. A production apparatus of silver halidephotographic emulsion according to claim 11, wherein the nucleus formingprocess, the nucleus growing process, the chemical sensitizing process,or the spectral sensitizing process is performed in the presence ofgelatin or chemically modified gelatin.
 14. A production apparatus ofsilver halide photographic emulsion according to claim 13, wherein asurface of a process liquid flow passage in the microreactor is formedof a material selected from the group consisting of nickel, aluminum,silver, gold, platinum, tantalum, stainless, hastelloy, titanium, fineceramics, special ceramics, and plastic.
 15. A production apparatus ofsilver halide photographic emulsion, which performs a nucleus formingprocess by using plural microreactors, performs a nucleus growingprocess by using plural microreactors, and performs a chemicalsensitizing process or a spectral sensitizing process by using pluralmicroreactors, wherein process liquids which have been forwarded to anext process from the plural microreactors for performing at least oneprocess of the plural microreactors for carrying out the nucleus formingprocess, the plural microreactors for carrying out the nucleus growingprocess, the plural microreactors for carrying out the chemicalsensitizing process, and the plural microreactors for carrying out thespectral sensitizing process are collected and are temporarily stored ina storage tank, and the process liquids are distributed and supplied tothe plural microreactors from the storage tank for performing the nextprocess.
 16. A production apparatus of silver halide photographicemulsion according to claim 15, wherein the nucleus forming process isperformed by bringing an aqueous halide solution into contact withsilver nitrate solution in a state of at least one laminar flow to formsilver halide grain nuclei.
 17. A production apparatus of silver halidephotographic emulsion according to claim 16, wherein the nucleus formingprocess, the nucleus growing process, the chemical sensitizing process,or the spectral sensitizing process is performed in the presence ofgelatin or chemically modified gelatin.
 18. A production apparatus ofsilver halide photographic emulsion according to claim 17, wherein asurface of a process liquid flow passage in the microreactor is formedof a material selected from the group consisting of nickel, aluminum,silver, gold, platinum, tantalum, stainless, hastelloy, titanium, fineceramics, special ceramics, and plastic.